Conductive polymer composition, substrate, and method for producing substrate

ABSTRACT

A conductive polymer composition containing: a composite containing a π-conjugated polymer (A) and a polymer (B) shown by the following general formula (2); H2O (D) for dispersing the composite; and a water-soluble organic solvent (C). This provides a composition which has favorable filterability and film formability, and which is capable of relieving acidity and forming a conductive film with high transparency. Moreover, since the H2O dispersion of the conductive polymer compound is mixed with an organic solvent, the surface tension and the contact angle are so low that leveling property on a substrate is imparted. The composition is usable in droplet-coating methods. Since an organic solvent having a higher boiling point than H2O is used as the organic solvent, the composition can avoid solid content precipitation around a nozzle and solid content precipitation due to drying between ejecting the liquid material from a nozzle tip and landing on a substrate.

TECHNICAL FIELD

The present invention relates to a conductive polymer composition, and asubstrate having a coating-type conductive film formed from theconductive polymer composition in an organic electroluminescent device.

BACKGROUND ART

A polymer having a conjugated double bond (a π-conjugated polymer) doesnot exhibit electrical conductivity by itself, but becomes anelectro-conductive polymer material by doping with an appropriate anionmolecule which causes electron or hole to move. (Hetero) aromaticpolymers such as polythiophene, polyselenophene, polytellurophene,polypyrrole, polyaniline, a mixture thereof, and the like, have beenused as the π-conjugated polymer. A sulfonic acid-based anion has mostfrequently been used as the anion molecule (dopant). This is because thesulfonic acid, which is a strong acid, interacts efficiently with theπ-conjugated polymer.

As the sulfonic acid-based anion dopant, sulfonic acid polymers such aspolyvinylsulfonic acid and polystyrenesulfonic acid (PSS) have widelybeen used (Patent Document 1). In addition, among such sulfonic acidpolymers, a vinyl perfluoroalkyl ether sulfonic acid represented byNafion® has been used for fuel cell applications.

The polystyrenesulfonic acid (PSS) which is a sulfonic acid homopolymerhas high efficiency in doping to the π-conjugated polymer since sulfonicacids are continuously present as the monomer units in the polymer mainchain, and it can improve dispersibility of the doped π-conjugatedpolymer in water. This is because hydrophilicity is retained by thepresence of sulfo groups excessively present in the PSS compared withthe doped portion, so that the dispersibility into water is dramaticallyimproved.

Polythiophene using the PSS as a dopant can be handled as a highlyconductive liquid material, and is thus expected as a coating-typetransparent electrode film material in place of ITO (indium tin oxide)used as a transparent electrode in organic EL, solar cell, etc. Whilethin-film devices including organic EL, solar cell, and so forth are insuch a trend that all the layers are made from coating-type material,high conductivity is not required, but it is desirable to applypolythiophene as a coating material which functions as an injectionlayer to reduce the carrier transfer load from an electrode to a carriertransfer layer.

When PSS having quite high hydrophilicity is added as a dopant to aπ-conjugated polymer having low hydrophilicity, the composite of theπ-conjugated polymer with the dopant is dispersed as particles in H₂O.This dispersion is applicable as a liquid material onto a substrate.After a substrate is coated with the composite, a film can be formed byheating with a hot air circulation furnace, hot plate, or the like, or afilm can be formed by IR or UV radiation, etc. Nevertheless, since thePSS having quite high hydrophilicity retains the moisture, a largeamount of moisture remains in the film after the treatment for the filmformation. After device preparation and sealing, the moisture volatizesand fills the device, for example, and consequently significantly lowersthe device performance in some cases. When the material is used for afilm (thin film) constituting, for example, an organic EL, the moistureremaining in the film and moisture absorbed from the external atmospherein the manufacturing process till sealing volatize or permeate anadjacent layer after constituent layers are laminated and sealed. Whenthe moisture condenses in the sealed device or in the film, this causesdefects and lowers the device functions such as decreased function ofthe light emitting layer and increased voltage for driving the devicedue to the moisture in the film. Consequently, there are problems suchas shortened device lifetime.

Hence, when a composite of a π-conjugated polymer with PSS as a dopantis used in the form of a H₂O dispersion as a transparent electrodematerial or hole injection layer material in an organic thin-film devicesuch as organic EL or solar cell, the remaining moisture degrades thedevice performance. Efforts have been made to disperse the composite inan organic solvent as an alternative solvent to H₂O; however, theaffinity to organic solvent is so low that it is difficult to obtain auniform dispersion.

Meanwhile, PEDOT-PSS, which has been studied for wide applications,absorbs light in the visible light range and the transmittance is low.Hence, this material has a difficulty in application to light-permeable,light emitting devices, and has natures such that dispersed particles ofthe composite in a liquid state are likely to aggregate. The filtrationpurification is difficult.

When a composite of a π-conjugated polymer with PSS as a dopant is usedfor a transparent electrode material or hole injection layer material inan organic thin-film device such as organic EL or solar cell, the thinfilm can be formed in a variety of ways. Examples of the film formationmethod include: coating with a spin coater, etc.; bar coating, dipping,comma coating, spray coating, roll coating, screen printing,flexographic printing, gravure printing, inkjet printing, etc. After asubstrate is coated, a conductive film can be formed by a heat treatmentwith a hot air circulation furnace, hot plate, or the like, by IR or UVradiation, etc. However, the filtration for removing the componentaggregates in the composition is problematic as described above. Coatingwithout filtration brings about problems: the coating is improperlycarried out due to the influence of these aggregates; even if a uniformfilm is obtained, the surface roughness is poor; and when the uniformfilm is employed for organic EL, solar cell, or the like having alaminate structure, problems such as impaired carrier transfer and shortcircuit are likely to occur due to such large surface unevenness orpinhole.

Moreover, when H₂O is used as the solvent for a composite of aπ-conjugated polymer with PSS as a dopant, since the surface tension ishigh, the contact angle is large regardless of whether a glass substrateor plastic substrate is coated. The aggregation occurs in the solutionafter the coating, or the solution is left adhering on the substrate asdroplets by the repelling on the substrate. Hence, it is necessary tolower the contact angle with respect to a substrate by lowering thesurface tension of the material, and to impart leveling property so thata uniform film can be formed. Particularly, in spray coating and inkjetprinting by spraying or blowing a liquid material, lowering the surfacetension and imparting leveling property are essential. Moreover, a solidcontent may be firmly attached around a nozzle, or the solid content mayprecipitate due to drying after the liquid material is ejected from thenozzle tip and before landing on the substrate. Hence, it is necessaryto use a less volatile solvent as a main solvent instead of H₂O, or tofurther add an agent for slowing the drying if the main solvent is H₂O.

When a glass substrate or plastic substrate is coated with a compositeof a π-conjugated polymer with PSS as a dopant, the main solvent is mostdesirably an organic solvent from the viewpoints of coatability and filmquality. Patent Documents 2 and 3 describe production of apolythiophene-polyanion complex in a water-free solvent orlow-water-content solvent. In these systems, H₂O as an initial solventis exchanged with another water-miscible organic solvent. For thispurpose, after an organic solvent is added, H₂O is removed bydistillation, for example. However, this procedure has the followingshortcomings: the distillation requires a two-stage process; the organicsolvent to be added has to be miscible with water; if the organicsolvent has a boiling point of roughly 150° C. or more, or if thepolythiophene-polyanion particle dispersion has high versatility,polymer modification occurs such that the conductivity is increased; inthe application as hole injection layer, there are such problems thatthe conductivity departs from the appropriate range; etc.

Meanwhile, in Patent Document 4, Otani et al. describe a method in whicha conductive polymer such as PEDOT is first dried and then re-dispersedin an organic solvent. Although isopropyl alcohol and γ-butyrolactoneare disclosed in Examples, this method requires a polar solvent forre-dissolution. This document does not disclose apolythiophene-polyanion composite. Concerning a polythiophene-polyanioncomposite, particularly PEDOT-PSS with PSS as a dopant, after removal ofH₂O, which is a solvent for chemical polymerization, a mechanicaltreatment, such as high-pressure dispersing, is required for there-dispersing into an organic solvent. Even after such treatment isperformed, when the composite is used for a transparent electrodematerial or hole injection layer material in an organic thin-film devicesuch as organic EL or solar cell, there is such a disadvantage thatdefects such as dark spots derived from the polymer aggregates arelikely to occur on the resulting film that transmits light. Theviscosity also tends to be high in comparison with the system with H₂Omain solvent. These disadvantages are considerably related to the filmformability as well as the luminance lifetime, durability, and yield inproduction of the organic thin-film device. This re-dispersion scheme isnot desirable because an appropriate dispersion in the PEDOT-PSS usagedoes not cause film thickness reduction due to the solid contentreduction by passing the dispersion through a filtration membrane of atleast 0.45 μm or less when the PEDOT-PSS is used.

Meanwhile, the synthesis method of a polythiophene-based conductivepolymer with PSS as a dopant, such as widely-applicable PEDOT-PSS, isknown, and numerous commercial products of the raw materials andmanufactured articles are available in the market. Accordingly, thepolythiophene-based conductive polymer is a suitable material applied toorganic thin-film devices such as organic EL and solar cell.Nevertheless, there are problems that: the transparency is poor due tovisible light absorption; the aggregation is highly likely in the H₂Odispersion state; the aggregation is further accelerated by mixing anorganic solvent, so that the viscosity is high and the filtrationpurification is difficult; after the film formation, plenty of moistureremains in the film; the film itself has poor surface roughness; anddefects are likely to occur by particles derived from the aggregates.Furthermore, in a state where no organic solvent is added to avoid theaggregation, the surface tension is so high that after the compositionis blown onto a substrate by employing a spray-type printer, the contactangle of landed droplets is high, and the leveling property is low.Consequently, a flat continuous film cannot be obtained, and a partialfilm or a sea-island structure is formed from the composition dropletson the substrate.

Patent Documents 5, 6, and 7 propose conductive polymer compositionsformed by using: a π-conjugated polymer formed of a repeating unitselected from thiophene, pyrrole, aniline, and polycyclic aromaticcompounds; and a dopant polymer incorporating a fluorinated acid unit.It is disclosed that a H₂O dispersion of the conductive polymer isobtained by combining H₂O, a precursor monomer of the π-conjugatedpolymer, a fluorinated acid polymer, and an oxidizing agent in anyorder. By introducing a fluorinated acid unit, the affinity of thefluorine atoms to organic solvents is imparted to the dopant polymer. Asa result, the composite including the π-conjugated polymer as a wholehas higher affinity to organic solvents and hydrophobic substratesurface, improving the dispersibility of the composite into organicsolvents and coatability onto hydrophobic substrates. Moreover,introducing a fluorinated acid unit into the dopant relieves the stronghydrophilicity observed from PSS, and thus the moisture remaining in thefilm is reduced after the film formation.

In Patent Document 6, the dopant polymer is constituted of a fluorinatedacid unit and such an acid unit as styrenesulfonic acid, which is aconstituent monomer of PSS. Nevertheless, the amount of H⁺ generatedfrom extra sulfonated terminals other than the sulfonated terminal fordoping the π-conjugated polymer is not controlled. In other words, in acase where every repeating unit of a dopant polymer (B) is a unit havinga sulfonated terminal, the repeating units constituting a π-conjugatedpolymer (A) are not doped therewith at a ratio of 1:1. Hence, thesulfonated terminals of the repeating units of the dopant polymer (B) ina non-doping state are present as free acids, so that the acidity of thematerial in a liquid state before film formation is very high. Due tothe influence of such high acidity, a problem occurs that surroundingmembers corrode progressively in the coating step. Furthermore, evenafter a film formed as a constituent of a thin-film device is dried, H⁺diffuses into the device structure through the adjacent layer or from aside surface of the laminate structure, bringing about problems such aschemical changes in constituent layers, and decreases in function,device performance as a whole, and durability. Against these problems,in Patent Document 7, an amphoteric ion compound is added to control thediffusion of H⁺ into such adjacent layer. Thereby, the compositecontaining a π-conjugated polymer formed of a repeating unit selectedfrom thiophene, pyrrole, aniline, and polycyclic aromatic compounds, anda dopant polymer incorporating a fluorinated acid unit is improved interms of dispersibility into an organic solvent and coatability onto asubstrate.

The composition described in Patent Document 7 has improveddispersibility into an organic solvent and improved coatability onto asubstrate as described above. In addition, spin coating method enablesformation of a flatter continuous film. Thus, the films formed by thismethod are applicable as, for example, an antistatic film for electronbeam resist, a transparent electrode layer and a hole injection layer inan organic EL device. Meanwhile, when a printing method with a spraycoater or a printing method to blow droplets onto a substrate likeinkjet printing is employed for an organic EL, solar cell, or the likehaving a laminate structure, the film formability is improved incomparison with a composite of a π-conjugated polymer with PSS as adopant, but problems such as coating spots, pinhole generation, andinsufficient film flatness are not completely solved. The resultingdevice has problems such as increased voltage, uneven light emission,and lowered durability. Moreover, when a solvent of the composition is100% H₂O, this H₂O volatizes in a spray coater and inkjet printing, thesolid content is firmly attached around the nozzle, or the solid contentprecipitates by drying after the liquid material is ejected from thenozzle tip and before landed on a substrate. Consequently, theprecipitate adheres to the film, causing defect problem in the organicEL device.

CITATION LIST Patent Literature

-   Patent Document 1: JP 2008-146913 A-   Patent Document 2: EP 1 373 356 A-   Patent Document 3: WO 2003/048228 A1-   Patent Document 4: JP 2005-068166 A-   Patent Document 5: JP 2008-546899 A-   Patent Document 6: JP 6483518 B-   Patent Document 7: JP 6450666 B

SUMMARY OF INVENTION Technical Problem

The present invention has been made in view of the above circumstances.An object of the present invention is to obtain a conductive polymercomposition having favorable filterability and film formability andbeing capable of: relieving acidity; forming a conductive film with hightransparency; imparting leveling property on a substrate; and beingapplicable in droplet-coating methods, such as spray coating and inkjetprinting.

Solution to Problem

To achieve the object, the present invention provides a conductivepolymer composition comprising:

a composite comprising

-   -   a π-conjugated polymer (A), and    -   a polymer (B) shown by the following general formula (2);

H₂O (D) for dispersing the composite; and

a water-soluble organic solvent (C),

wherein R¹ represents a hydrogen atom or a methyl group; Z representsany of a phenylene group, a naphthylene group, an ester group, an ethergroup, an amino group, and an amide group; when Z is a phenylene groupor a naphthylene group, R² represents any of a single bond and a linear,branched, or cyclic hydrocarbon group having 1 to 12 carbon atomsoptionally having one or both of an ester group and an ether group; whenZ is an ester group, an ether group, an amino group, or an amide group,R² represents any of a single bond and a linear, branched, or cyclichydrocarbon group having 1 to 14 carbon atoms optionally having an ethergroup; “m” represents any one of 1 to 3; R³, R⁵, and R⁷ eachindependently represent a hydrogen atom or a methyl group; R⁴ and R⁶each independently represent any of a single bond and a linear,branched, or cyclic hydrocarbon group having 1 to 12 carbon atomsoptionally having one or both of an ether group and an ester group; R⁸represents any of a single bond, a methylene group, an ethylidene group,an isopropylidene group, an ether group, an ester group, an amino group,an amide group, and a linear, branched, or cyclic hydrocarbon grouphaving 1 to 12 carbon atoms optionally containing an ether group, anester group, an amino group, an amide group, or a heteroatom, and theamino groups and the amide groups each optionally contain any of ahydrogen atom and a linear, branched, or cyclic hydrocarbon group having1 to 12 carbon atoms optionally containing a heteroatom; X₁ and X₂ eachindependently represent any of a single bond, a phenylene group, anaphthylene group, an ether group, an ester group, and an amide group;X₃ represents any of a single bond, an ether group, and an ester group;Rf₁ represents a fluorine atom or a trifluoromethyl group; “a”, b1, b2,and b3 satisfy 0<a<1.0, 0≤b1<1.0, 0≤b2<1.0, 0≤b3<1.0, and0<b1+b2+b3<1.0; and “n” represents an integer of 1 to 4.

Incorporating (A), (B), (C), and (D) as described above enables theconductive polymer composition to have favorable filterability and filmformability, to relieve acidity, and to form a conductive film havinghigh transparency. Moreover, as the H₂O dispersion of the composition ismixed with a water-soluble organic solvent, the surface tension and thecontact angle are so low that leveling property on a substrate isimparted. Further, the composition is applicable in droplet-coatingmethods, such as spray coating and inkjet printing.

Moreover, the inventive composition preferably has a surface tension ina range of 20 to 50 mN/m.

With such a low surface tension, when the composition is blown onto asubstrate by employing a spray-type printer, the landed droplets willnot have high contact angle, preventing the composition droplets fromforming a sea-island structure or a partial film on the substrate.

The component (C) preferably comprises an organic solvent (C1) having aboiling point of 120° C. or more and/or an organic solvent (C2) having aboiling point of less than 120° C. such that 1.0 wt %≤(C1)+(C2)≤50.0 wt% is satisfied relative to a total of the components (A), (B), and (D).

In this case, the components (C1) and (C2) are preferably selected fromalcohols, ethers, esters, ketones, and nitriles each of which has 1 to 7carbon atoms.

In the present invention, such organic solvents are usable.

The repeating unit “a” in the component (B) preferably comprises one ormore selected from repeating units a1 to a4 shown by the followinggeneral formulae (4-1) to (4-4),

wherein R¹⁶, R¹⁷, R¹⁸, and R¹⁹ each independently represent a hydrogenatom or a methyl group; Rn represents any of a single bond and a linear,branched, or cyclic hydrocarbon group having 1 to 14 carbon atomsoptionally having an ether group; R¹⁵ represents any of a single bond, amethylene group, an ethylidene group, an isopropylidene group, an ethergroup, an ester group, an amino group, an amide group, and a linear,branched, or cyclic hydrocarbon group having 1 to 12 carbon atomsoptionally containing an ether group, an ester group, an amino group, anamide group, or a heteroatom, and the amino groups and the amide groupseach optionally contain any of a hydrogen atom and a linear, branched,or cyclic hydrocarbon group having 1 to 12 carbon atoms optionallycontaining a heteroatom; Y represents any of an ether group, an estergroup, an amino group, and an amide group, and the amino group and theamide group each optionally contain any of a hydrogen atom and a linear,branched, or cyclic hydrocarbon group having 1 to 12 carbon atomsoptionally containing a heteroatom; “m” represents any one of 1 to 3;and a1, a2, a3, and a4 satisfy 0≤a1<1.0, 0≤a2<1.0, 0≤a3<1.0, 0≤a4<1.0,and 0<a1+a2+a3+a4<1.0.

Further, in this case, the repeating unit b1 in the component (B)preferably comprises one or more selected from repeating units b1′ tob4′ shown by the following general formulae (5-1) to (5-4),

wherein R²¹, R²², R²³, and R²⁴ each independently represent a hydrogenatom or a methyl group; and b′1, b′2, b′3, and b′4 satisfy 0≤b′1<1.0,0≤b′2<1.0, 0≤b′3<1.0, 0≤b′4<1.0, and 0<b′1+b′2+b′3+b′4<1.0.

The component (B) preferably contains the repeating unit(s) as describedabove. These enhance the filterability and film formability of theconductive polymer composition, the coatability onto organic andinorganic substrates, and the transmittance after the film formation.Additionally, the effect of reducing residual moisture in the formedfilm will be exhibited.

Additionally, in this case, the component (B) may further comprise arepeating unit “c” shown by the following general formula (6),

wherein “c” satisfies 0<c<1.0.

By incorporating such repeating unit “c”, it is possible to adjust theconductivity of the film appropriately for intended applications and forefficient function demonstration when a device constituent layer isformed.

Furthermore, the component (B) preferably has a weight-average molecularweight in a range of 1,000 to 500,000.

When the weight-average molecular weight is 1,000 or more, the heatresistance is excellent, and the uniformity of the solution containingthe composite with the component (A) is favorable. Meanwhile, when theweight-average molecular weight is 500,000 or less, the viscosity is notincreased too much, the workability is favorable, and the dispersibilityinto water and an organic solvent is not lowered.

Moreover, in this case, the component (A) is preferably a material inwhich at least one precursor monomer selected from the group consistingof pyrrole, thiophene, selenophene, tellurophene, aniline, polycyclicaromatic compounds, and derivatives thereof is polymerized.

Such monomers are easily polymerized, and the stability in air isfavorable. Hence, the component (A) can be easily synthesized.

The inventive conductive polymer composition preferably comprises acomponent (E) shown by the following general formula (3).

In the formula, R²⁰¹ and R²⁰² each independently represent any of ahydrogen atom, a heteroatom, and a linear, branched, or cyclicmonovalent hydrocarbon group having 1 to 20 carbon atoms optionallyhaving a heteroatom; R²⁰³ and R²⁰⁴ each independently represent any of ahydrogen atom and a linear, branched, or cyclic monovalent hydrocarbongroup having 1 to 20 carbon atoms optionally having a heteroatom; R²⁰¹and R²⁰³, or R²⁰¹ and R²⁰⁴, are optionally bonded to each other to forma ring; L represents a linear, branched, or cyclic tetravalent organicgroup having 1 to 20 carbon atoms optionally having a heteroatom; andwhen L has a heteroatom, the heteroatom is optionally an ion.

When the conductive polymer composition containing the component (E) isused to form a film as an electrode or hole injection layer of athin-film stacked device such as organic EL and solar cell, the aciddiffusion to an adjacent layer and another constituent layer of thelaminate structure is suppressed. This makes it possible to relieve theinfluence of the acid. Moreover, when the inventive conductive polymercomposition contains the component (E) and this conductive polymercomposition is used to form a film as a constituent of a thin-filmdevice having a laminate structure on a material to be processed, theacid diffusion to an adjacent layer and another constituent layer of thelaminate structure device is further suppressed. Thus, the acidinfluence can be further relieved.

Further, in this case, the component (E) is preferably contained in anamount of 1 part by mass to 50 parts by mass based on 100 parts by massof the composite of the component (A) with the component (B).

Preferably, the inventive composition further comprises a nonionicsurfactant.

Such a component can further enhance the coatability onto a material tobe processed, such as a substrate.

Additionally, in this case, the nonionic surfactant is preferablycontained in an amount of 1 part by mass to 15 parts by mass based on100 parts by mass of the composite of the component (A) with thecomponent (B).

Such a composition has more favorable coatability onto a material to beprocessed, such as a substrate. The film to be formed also has morefavorable surface flatness.

In addition, the inventive conductive polymer composition is preferablyused to form a hole injection layer of an organic EL device.

The conductive film formed from the inventive conductive polymercomposition is excellent in conductivity, hole injectability, andtransparency, and thus can function as a transparent electrode layer orhole injection layer of a thin film-stacked device, such as organic ELand solar cell.

The present invention also provides a substrate comprising an organic ELdevice, wherein the organic EL device comprises a hole injection layerformed from the above-described conductive polymer composition.

In this manner, a conductive film can be formed by coating a substrateor the like with the inventive conductive polymer composition. Thismakes it possible to provide a substrate on which a hole injection layeris formed as the conductive film in an organic EL device.

Furthermore, the present invention provides a method for producing thesubstrate, comprising a step of applying the above-described conductivepolymer composition by employing a spray coater or inkjet printing.

The substrate of the present invention can be produced by such a method.

Advantageous Effects of Invention

As described above, the inventive conductive polymer composition has lowviscosity, favorable filterability, and good film formability by coatingon inorganic and organic substrates, and is also capable of providing acontinuous film with few defects even when a spray coater or an inkjetprinter is used. Moreover, residual moisture in the film is efficientlyremoved during the film formation by the influence of fluorine atomspresent in the repeating units “a” and “b” in the dopant polymer as thecomponent (B). The film to be formed can be a conductive film havingfavorable transparency, flatness, and electrical conductivity or holeinjection efficiency. Further, in the component (B), the repeating unit“b” containing a sulfo group is copolymerized with the non-dopingfluorinated unit “a” having no sulfonated terminal. The use of thispolymer as a dopant to form a composite with the component (A) decreasesextra non-doping sulfonated terminals, consequently generating fewer H⁺.When the inventive conductive polymer composition is employed as aconstituent film of a thin film-stacked device, it is possible tosuppress the influence of H⁺ on other constituent layers. Furthermore,the conductive film formed from the inventive conductive polymercomposition is excellent in conductivity, hole injection efficiency,transparency, etc., and can reduce moisture volatilization from thefilm, aggregation, and so forth when employed as a constituent film of athin film-stacked device. Accordingly, such a conductive film caneffectively function as a transparent electrode layer or hole injectionlayer of such a thin film-stacked device.

DESCRIPTION OF EMBODIMENTS

As noted above, it has been desired to develop a material for forming aconductive film, the material having: low viscosity, favorablefilterability, and good coating-film formability on inorganic andorganic substrates; ability to form a continuous film with few defectseven when a spray coater or an inkjet printer is used; ability to form aconductive film with high transparency and favorable flatness; andability to efficiently remove residual moisture in such films.

The present inventors have intensively studied the problems, andconsequently found the following facts. Specifically, in place ofpolystyrenesulfonic acid homopolymer (PSS) widely used as a dopant for aconductive polymer material, a dopant polymer is prepared bycopolymerizing a non-doping fluorinated unit “a” with a repeating unit“b” including a repeating unit with a sulfo group fluorinated at theα-position, for example. Further, a H₂O dispersion of a conductivepolymer material using this dopant polymer is mixed with a water-solubleorganic solvent. A conductive polymer composition thus obtained hasfavorable filterability and favorable ability to form a continuous filmwith few defects on an inorganic substrate even when a spray coater oran inkjet printer is used. Moreover, the conductive polymer compositioncan form a conductive film having high transparency, high flatness, andlittle residual moisture in the formed film. Further, favorable resultshave been obtained in the performance evaluations of the conductivepolymer composition mounted as a constituent layer of an organic ELdevice. These findings have led to the completion of the presentinvention.

Specifically, the present invention is a conductive polymer compositioncomprising:

a composite comprising

-   -   a π-conjugated polymer (A), and    -   a polymer (B) shown by the following general formula (2);

H₂O (D) for dispersing the composite; and

a water-soluble organic solvent (C),

wherein R¹ represents a hydrogen atom or a methyl group; Z representsany of a phenylene group, a naphthylene group, an ester group, an ethergroup, an amino group, and an amide group; when Z is a phenylene groupor a naphthylene group, R² represents any of a single bond and a linear,branched, or cyclic hydrocarbon group having 1 to 12 carbon atomsoptionally having one or both of an ester group and an ether group; whenZ is an ester group, an ether group, an amino group, or an amide group,R² represents any of a single bond and a linear, branched, or cyclichydrocarbon group having 1 to 14 carbon atoms optionally having an ethergroup; “m” represents any one of 1 to 3; R³, R⁵, and R⁷ eachindependently represent a hydrogen atom or a methyl group; R⁴ and R⁶each independently represent any of a single bond and a linear,branched, or cyclic hydrocarbon group having 1 to 12 carbon atomsoptionally having one or both of an ether group and an ester group; R⁸represents any of a single bond, a methylene group, an ethylidene group,an isopropylidene group, an ether group, an ester group, an amino group,an amide group, and a linear, branched, or cyclic hydrocarbon grouphaving 1 to 12 carbon atoms optionally containing an ether group, anester group, an amino group, an amide group, or a heteroatom, and theamino groups and the amide groups each optionally contain any of ahydrogen atom and a linear, branched, or cyclic hydrocarbon group having1 to 12 carbon atoms optionally containing a heteroatom; X₁ and X₂ eachindependently represent any of a single bond, a phenylene group, anaphthylene group, an ether group, an ester group, and an amide group;X₃ represents any of a single bond, an ether group, and an ester group;Rf₁ represents a fluorine atom or a trifluoromethyl group; “a”, b1, b2,and b3 satisfy 0<a<1.0, 0≤b1<1.0, 0≤b3<1.0, and 0<b1+b2+b3<1.0; and “n”represents an integer of 1 to 4.

Hereinafter, the present invention will be described in detail, but thepresent invention is not limited thereto.

[(A) π-Conjugated Polymer]

The inventive conductive polymer composition contains a π-conjugatedpolymer as a component (A). This component (A) may be a polymercontaining a precursor monomer (organic monomer molecule) for forming aπ-conjugated chain (a structure in which a single bond and a double bondare alternately continued).

Examples of such a precursor monomer include monocyclic aromatics, suchas pyrroles, thiophenes, thiophene vinylenes, selenophenes,tellurophenes, phenylenes, phenylene vinylenes, and anilines; polycyclicaromatics, such as acenes; acetylenes; etc. A homopolymer or a copolymerof these monomers can be used as the component (A).

Among the monomers, from the viewpoints of easiness in polymerizationand stability in air, pyrrole, thiophene, selenophene, tellurophene,aniline, polycyclic aromatic compounds, and derivatives thereof arepreferable, and pyrrole, thiophene, aniline, and derivatives thereof areparticularly preferable.

In addition, the component (A) can give sufficient conductivity evenwhen the monomer constituting the n-conjugated polymer is notsubstituted. Nevertheless, for higher conductivity, a monomersubstituted by an alkyl group, a carboxyl group, a sulfo group, analkoxy group, a hydroxyl group, a cyano group, a halogen atom, or thelike may be used.

Specific examples of the monomers of pyrroles, thiophenes, and anilinesinclude pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole,3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole,3-dodecylpyrrole, 3,4-dimethylpyrrole, 3,4-dibutylpyrrole,3-carboxypyrrole, 3-methyl carboxypyrrole,3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole,3-hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole,3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole; thiophene,3-methylthiophene, 3-ethylthiophene, 3-propylthiophene,3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene,3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene,3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene,3-phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene,3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene,3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene,3-octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene,3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene,3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene,3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene,3,4-dioctyloxythiophene, 3,4-didecyloxythiophene,3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene,3,4-propylenedioxythiophene, 3,4-butenedioxythiophene,3-methyl-4-methoxythiophene, 3-methyl-4-ethoxythiophene,3-carboxythiophene, 3-methyl-4-carboxythiophene,3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene;aniline, 2-methylaniline, 3-isobutylaniline, 2-methoxyaniline,2-ethoxyaniline, 2-anilinesulfonic acid, 3-anilinesulfonic acid; etc.

Particularly, a (co)polymer containing one or two selected from pyrrole,thiophene, N-methylpyrrole, 3-methylthiophene, 3-methoxythiophene, and3,4-ethylenedioxythiophene is suitably used from the viewpoints of aresistance value and reactivity. Moreover, a homopolymer of pyrrole or3,4-ethylenedioxythiophene is more preferable because the conductivityis high.

For a practical reason, the number of these repeating units repeated ispreferably in a range of 2 to 20, more preferably 6 to 15. The molecularweight is preferably about 130 to 5000.

[(B) Dopant Polymer]

The inventive conductive polymer composition contains a dopant polymeras a component (B). This dopant polymer as the component (B) is astrongly acidic polyanion containing repeating units “a” and “b” shownby the following general formula (2). A monomer for forming therepeating unit “a” is shown by the following general formula (1).

In the formulae, R¹ represents a hydrogen atom or a methyl group. Zrepresents any of a phenylene group, a naphthylene group, an estergroup, an ether group, an amino group, and an amide group. When Z is aphenylene group or a naphthylene group, R² represents any of a singlebond and a linear, branched, or cyclic hydrocarbon group having 1 to 12carbon atoms optionally having one or both of an ester group and anether group. When Z is an ester group, an ether group, an amino group,or an amide group, R² represents any of a single bond and a linear,branched, or cyclic hydrocarbon group having 1 to 14 carbon atomsoptionally having an ether group. “m” represents any one of 1 to 3. R³,R⁵, and R⁷ each independently represent a hydrogen atom or a methylgroup. R⁴ and R⁶ each independently represent any of a single bond and alinear, branched, or cyclic hydrocarbon group having 1 to 12 carbonatoms optionally having one or both of an ether group and an estergroup. R⁸ represents any of a single bond, a methylene group, anethylidene group, an isopropylidene group, an ether group, an estergroup, an amino group, an amide group, and a linear, branched, or cyclichydrocarbon group having 1 to 12 carbon atoms optionally containing anether group, an ester group, an amino group, an amide group, or aheteroatom; the amino groups and the amide groups each optionallycontain any of a hydrogen atom and a linear, branched, or cyclichydrocarbon group having 1 to 12 carbon atoms optionally containing aheteroatom. X₁ and X₂ each independently represent any of a single bond,a phenylene group, a naphthylene group, an ether group, an ester group,and an amide group. X₃ represents any of a single bond, an ether group,and an ester group. Rf₁ represents a fluorine atom or a trifluoromethylgroup. “a”, b1, b2, and b3 satisfy 0<a<1.0, 0≤b1<1.0, 0≤b2<1.0,0≤b3<1.0, and 0<b1+b2+b3<1.0. “n” represents an integer of 1 to 4.

In the component (B), the repeating unit “a” preferably includes one ormore selected from repeating units a1 to a4 shown by the followinggeneral formulae (4-1) to (4-4).

In the formulae, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ each independently represent ahydrogen atom or a methyl group. R²⁰ represents any of a single bond anda linear, branched, or cyclic hydrocarbon group having 1 to 14 carbonatoms optionally having an ether group. R¹⁵ represents any of a singlebond, a methylene group, an ethylidene group, an isopropylidene group,an ether group, an ester group, an amino group, an amide group, and alinear, branched, or cyclic hydrocarbon group having 1 to 12 carbonatoms optionally containing an ether group, an ester group, an aminogroup, an amide group, or a heteroatom; the amino groups and the amidegroups each optionally contain a hydrogen atom. Y represents any of anether group, an ester group, an amino group, and an amide group; theamino group and the amide group each optionally contain any of ahydrogen atom and a linear, branched, or cyclic hydrocarbon group having1 to 12 carbon atoms optionally containing a heteroatom. “m” representsany one of 1 to 3. a1, a2, a3, and a4 satisfy 0≤a1<1.0, 0≤a2<1.0,0≤a3<1.0, 0≤a4<1.0, and 0<a1+a2+a3+a4<1.0.

In the component (B), the higher the content of the repeating unit “a”relative to the repeating units “b”, the more clearly the effects of thepresent invention are exhibited. The content percentage is preferably20≤a≤60, so that the effects of the present invention are sufficientlyobtained. From the viewpoints of the conductivity and the stability ofthe composite of (A) and (B), the content percentage of the repeatingunit “a” is further preferably 20≤a≤40. Specifically, in order toachieve conductivity for exhibiting sufficient functions as anelectrode, or achieve hole injection efficiency for exhibitingsufficient functions as a hole injection layer, reasonable ranges are20≤a≤40 and 60≤b≤80, preferably 20≤a≤40 and 60≤b+c≤80; in this case,c≤40 is preferable. “c” will be described later.

A monomer for providing the repeating unit “a” can be specificallyexemplified by the following.

As the repeating unit b1, the component (B) preferably contains one ormore selected from repeating units b′1 to b′4 shown by the followinggeneral formulae (5-1) to (5-4).

In the formulae, R²¹, R²², R²³, and R²⁴ each independently represent ahydrogen atom or a methyl group. b′1, b′2, b′3, and b′4 satisfy0≤b′1<1.0, 0≤b′2<1.0, 0≤b′3<1.0, 0≤b′4<1.0, and 0<b′1+b′2+b′3+b′4<1.0.

A monomer for providing the repeating unit b1 can be specificallyexemplified by the following.

In the formulae, R³ is as defined above.

A monomer for providing the repeating unit b2 can be specificallyexemplified by the following.

In the formulae, R⁵ is as defined above.

A monomer for providing the repeating unit b3 can be specificallyexemplified by the following.

In the formulae, R⁷ is as defined above.

The component (B) can further contain a repeating unit “c” shown by thefollowing general formula (6).

“c” satisfies 0<c<1.0.

A monomer for providing the repeating unit “c” can be specificallyexemplified by the following.

Furthermore, the dopant polymer as the component (B) may have arepeating unit “d” other than the repeating units “a” to “c”. Examplesof the repeating unit “d” can include repeating units based on styrene,vinylnaphthalene, vinylsilane, acenaphthylene, indene, vinylcarbazole,etc.

A monomer for providing the repeating unit “d” can be specificallyexemplified by the following.

As a method for synthesizing the dopant polymer of the component (B),for example, desired monomers among the monomers providing the repeatingunits “a” to “d” may be subjected to polymerization under heating in anorganic solvent by adding a radical polymerization initiator to obtain adopant polymer which is a (co)polymer.

The organic solvent to be used at the time of the polymerization may beexemplified by toluene, benzene, tetrahydrofuran, diethyl ether,dioxane, cyclohexane, cyclopentane, methyl ethyl ketone,γ-butyrolactone, etc.

The radical polymerization initiator may be exemplified by2,2′-azobisisobutyronitrile (AIBN),2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl2,2′-azobis(2-methylpropionate), benzoyl peroxide, lauroyl peroxide,etc.

The reaction temperature is preferably 50 to 80° C. The reaction time ispreferably 2 to 100 hours, more preferably 5 to 20 hours.

In the dopant polymer as the component (B), the monomer for providingthe repeating unit “a” may be either one kind or two or more kinds. Itis preferable to use a methacrylic type monomer and a styrene typemonomer in combination to heighten polymerizability.

When two or more kinds of the monomers for providing the repeating unit“a” are used, the monomers may be randomly copolymerized, or may becopolymerized in block. When the block copolymerized polymer (blockcopolymer) is made, the repeating unit portions of two or more kinds ofthe repeating unit “a” aggregate, whereby a specific structure isgenerated around the dopant polymer, and as a result, a merit ofimproving electric conductivity can also be expected.

In addition, the monomers providing the repeating units “a” to “c” maybe randomly copolymerized, or may be copolymerized in block. In thiscase also, a merit of improving conductivity can be expected by forminga block copolymer, as in the case of the repeating unit “a”.

When the random copolymerization is carried out by the radicalpolymerization, it is a general method that monomers to be copolymerizedand a radical polymerization initiator are mixed and polymerized underheating. Polymerization is started in the presence. of a first monomerand a radical polymerization initiator, and a second monomer is addedlater. Thereby, one side of the polymer molecule has a structure inwhich the first monomer is polymerized, and the other side has astructure in which the second monomer is polymerized. In this case,however, the repeating units of the first and second monomers aremixedly present in the intermediate portion, and the form is differentfrom that of the block copolymer. For forming the block copolymer by theradical polymerization, living radical polymerization is preferablyused.

In the living radical polymerization method called as the RAFTpolymerization (Reversible Addition Fragmentation chain Transferpolymerization), the radical at the polymer end is always living, sothat it is possible to form a di-block copolymer with a block of therepeating unit of the first monomer and a block of the repeating unit ofthe second monomer by: starting the polymerization with the firstmonomer, and adding the second monomer when the first monomer isconsumed. Further, a tri-block copolymer can also be formed by: startingthe polymerization with the first monomer, adding the second monomerwhen the first monomer is consumed, and then adding a third monomer.

When the RAFT polymerization is carried out, there is a characteristicthat a narrow dispersion polymer whose molecular weight distribution(dispersity) is narrow is formed. In particular, when the RAFTpolymerization is carried out by adding the monomers at a time, apolymer having a narrower molecular weight distribution can be formed.

Note that the dopant polymer as the component (B) has a molecular weightdistribution (Mw/Mn) of preferably 1.0 to 2.0, particularly preferably anarrow dispersity of 1.0 to 1.5. With a narrow dispersity, it ispossible to prevent a decrease in the transmittance of a conductive filmformed from the conductive polymer composition using such dopantpolymer.

For carrying out the RAFT polymerization, a chain transfer agent isnecessary. Specific examples thereof include2-cyano-2-propylbenzothioate, 4-cyano-4-phenylcarbonothioylthiopentanoicacid, 2-cyano-2-propyl dodecyl trithiocarbonate, 4-cyano[(dodecylsulfanylthiocarbonyl) sulfanyl]pentanoic acid,2-(dodecylthiocarbonothioylthio)-2-methylpropanoic acid, cyanomethyldodecyl thiocarbonate, cyanomethyl methyl(phenyl)carbamothioate,bis(thiobenzoyl)disulfide, andbis(dodecylsulfanylthiocarbonyl)disulfide. Among these,2-cyano-2-propylbenzothioate is particularly preferable.

The dopant polymer as the component (B) has a weight-average molecularweight in a range of preferably 1,000 to 500,000, more preferably 2,000to 200,000. When the weight-average molecular weight is 1,000 or more,the heat resistance is excellent, and the uniformity of the compositesolution with the component (A) does not deteriorate. Meanwhile, whenthe weight-average molecular weight is 500,000 or less, the viscosity isnot increased too much, the workability is favorable, and thedispersibility into water and an organic solvent is favorable.

Incidentally, the weight-average molecular weight (Mw) is a measuredvalue in terms of polyethylene oxide, polyethylene glycol, orpolystyrene, by gel permeation chromatography (GPC) using water,dimethylformamide (DMF), or tetrahydrofuran (THF) as a solvent.

Note that, as a monomer constituting the dopant polymer of the component(B), a monomer having a sulfo group may be used. Alternatively, thepolymerization reaction may be carried out using a monomer which is alithium salt, a sodium salt, a potassium salt, an ammonium salt, or asulfonium salt of a sulfo group; after the polymerization, the resultantis changed to a sulfo group by using an ion exchange resin.

[Composite of Components (A) and (B)]

The inventive conductive polymer composition contains the compositecontaining: the π-conjugated polymer as the component (A); and thedopant polymer as the component (B). The dopant polymer of the component(B) is coordinated to the π-conjugated polymer of the component (A) toform the composite.

Preferably, the composite used in the present invention is capable ofdispersing in H₂O and has affinity to an organic solvent. The compositecan improve the continuous-film formability and the film flatness on ahighly hydrophobic inorganic or organic substrate when a spray coaterand an inkjet printer are used.

(Composite Production Method)

The composite of the components (A) and (B) can be obtained, forexample, by adding a raw-material monomer of the component (A)(preferably, pyrrole, thiophene, aniline, or a derivative monomerthereof) into an aqueous solution of the component (B) or a mixturesolution of water and an organic solvent with the component (B), andadding an oxidizing agent and, if necessary, an oxidizing catalystthereto, to carry out oxidative polymerization.

The oxidizing agent and the oxidizing catalyst which can be used may be:a peroxodisulfate (persulfate), such as ammonium peroxodisulfate(ammonium persulfate), sodium peroxodisulfate (sodium persulfate), andpotassium peroxodisulfate (potassium persulfate); a transition metalcompound, such as ferric chloride, ferric sulfate, and cupric chloride;a metal oxide, such as silver oxide and cesium oxide; a peroxide, suchas hydrogen peroxide and ozone; an organic peroxide, such as benzoylperoxide; oxygen, etc.

As the reaction solvent to be used for carrying out the oxidativepolymerization, water or a mixed solvent of water and an organic solventmay be used. The organic solvent herein used is preferably an organicsolvent which is miscible with water, and can dissolve or disperse thecomponents (A) and (B). Examples of the solvent include polar solvents,such as N-methyl-2-pyrrolidone, N,N′-dimethylformamide,N,N′-dimethylacetamide, dimethylsulfoxide, and hexamethylenephosphotriamide; alcohols, such as methanol, ethanol, propanol, andbutanol; polyhydric aliphatic alcohols, such as ethylene glycol,propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butyleneglycol, D-glucose, D-glucitol, isoprene glycol, butanediol,1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and neopentyl glycol;carbonate compounds, such as ethylene carbonate and propylene carbonate;cyclic ether compounds, such as dioxane and tetrahydrofuran; linearethers, such as dialkyl ether, ethylene glycol monoalkyl ether, ethyleneglycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycoldialkyl ether, polyethylene glycol dialkyl ether, and polypropyleneglycol dialkyl ether; heterocyclic compounds, such as3-methyl-2-oxazolidinone; nitrile compounds, such as acetonitrile,glutaronitrile, methoxyacetonitrile, propionitrile, and benzonitrile;etc. One of these organic solvents may be used singly, or two or morekinds thereof may be used in mixture. A formulation ratio of theseorganic solvents miscible with water is preferably 50 mass % or lessbased on the whole reaction solvent.

In addition, an anion which is capable of doping the component (A) ofthe π-conjugated polymer may be used in combination other than thecomponent (B) of the dopant polymer. Such an anion is preferably anorganic acid from the viewpoints of, for example, adjusting de-dopingcharacteristics from the π-conjugated polymer, dispersibility of theconductive polymer composite, heat resistance, and environmentalresistance characteristics. Examples of the organic acid include anorganic carboxylic acid, phenols, an organic sulfonic acid, etc.

As the organic carboxylic acid, a material in which one or two or morecarboxyl groups are contained in an aliphatic, an aromatic, acycloaliphatic, or the like may be used. Examples thereof include formicacid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleicacid, fumaric acid, malonic acid, tartaric acid, citric acid, lacticacid, succinic acid, monochloroacetic acid, dichloroacetic acid,trichloroacetic acid, trifluoroacetic acid, nitroacetic acid,triphenylacetic acid, etc.

Examples of the phenols include phenols, such as cresol, phenol, andxylenol.

As the organic sulfonic acid, a material in which one or two or moresulfonic acid groups are contained in an aliphatic, an aromatic, acycloaliphatic, or the like may be used. Examples of the organicsulfonic acid containing one sulfonic acid group can include sulfonicacid compounds containing a sulfonic acid group, such as methanesulfonicacid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonicacid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonicacid, 1-nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonicacid, 1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid,2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid,trifluoromethanesulfonic acid, colistinmethanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid, aminomethanesulfonic acid,1-amino-2-naphthol-4-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid,3-aminopropanesulfonic acid, N-cyclohexyl-3-aminopropanesulfonic acid,benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid,ethylbenzenesulfonic acid, propylbenzenesulfonic acid,butylbenzenesulfonic acid, pentylbenzenesulfonic acid,hexylbenzenesulfonic acid, heptylbenzenesulfonic acid,octylbenzenesulfonic acid, nonylbenzenesulfonic acid,decylbenzenesulfonic acid, undecylbenzenesulfonic acid,dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid,hexadecylbenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid,dipropylbenzenesulfonic acid, butylbenzenesulfonic acid,4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid,m-aminobenzenesulfonic acid, 4-amino-2-chlorotoluene-5-sulfonic acid,4-amino-3-methylbenzene-1-sulfonic acid,4-amino-5-methoxy-2-methylbenzenesulfonic acid,2-amino-5-methylbenzene-1-sulfonic acid, 4-aminomethylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid,4-amino-3-methylbenzene-1-sulfonic acid,4-acetamido-3-chlorobenzenesulfonic acid, 4-chloro nitrobenzenesulfonicacid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid,methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid,butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid,dimethylnaphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid,8-chloronaphthalene-1-sulfonic acid, naphthalenesulfonic acid formalinpolycondensate, and melaminesulfonic acid formalin polycondensate.

Examples of the organic sulfonic acid containing two or more sulfonicacid groups can include ethanedisulfonic acid, butanedisulfonic acid,pentanedisulfonic acid, decanedisulfonic acid, m-benzenedisulfonic acid,o-benzenedisulfonic acid, p-benzenedisulfonic acid, toluenedisulfonicacid, xylenedisulfonic acid, chlorobenzenedisulfonic acid,fluorobenzenedisulfonic acid, aniline-2,4-disulfonic acid,aniline-2,5-disulfonic acid, dimethylbenzenedisulfonic acid,diethylbenzenedisulfonic acid, dibutylbenzenedisulfonic acid,naphthalenedisulfonic acid, methylnaphthalenedisulfonic acid,ethylnaphthalenedisulfonic acid, dodecylnaphthalenedisulfonic acid,pentadecylnaphthalenedisulfonic acid, butylnaphthalenedisulfonic acid,2-amino-1,4-benzenedisulfonic acid, 1-amino-3,8-naphthalenedisulfonicacid, 3-amino-1,5-naphthalenedisulfonic acid,8-amino-1-naphthol-3,6-disulfonic acid,4-amino-5-naphthol-2,7-disulfonic acid, anthracenedisulfonic acid,butylanthracenedisulfonic acid,4-acetamido-4′-isothio-cyanatostilbene-2,2′-disulfonic acid,4-acetamido-4′-isothiocyanatostilbene-2,2′-disulfonic acid,4-acetamido-4′-maleimidylstilbene-2,2′-disulfonic acid,1-acetoxypyrene-3,6,8-trisulfonic acid,7-amino-1,3,6-naphthalenetrisulfonic acid,8-aminonaphthalene-1,3,6-trisulfonic acid,3-amino-1,5,7-naphthalenetrisulfonic acid, etc.

These anions other than the component (B) may be added to the solutioncontaining the raw-material monomer of the component (A), the component(B), an oxidizing agent and/or an oxidative polymerization catalystbefore polymerization of the component (A), or may be added to thecomposite containing the components (A) and (B) after thepolymerization.

The thus obtained composite of the components (A) and (B) can be used,if necessary, after subjected to fine pulverization with a homogenizer,a ball mill, or the like.

For fine pulverization, a mixing-dispersing machine which can providehigh shearing force is preferably used. Examples of themixing-dispersing machine include a homogenizer, a high-pressurehomogenizer, a bead mill, etc. Among these, a high-pressure homogenizeris preferable.

Specific examples of the high-pressure homogenizer include Nanovatermanufactured by Yoshida Kikai Co., Ltd., Microfluidizer manufactured byPowrex Corp., Artimizer manufactured by Sugino Machine Limited., etc.

Examples of a dispersing treatment using the high-pressure homogenizerinclude a treatment in which the composite solution before subjecting tothe dispersing treatment is subjected to counter-collision with highpressure; a treatment in which it is passed through an orifice or slitwith high pressure; and other similar methods.

Before or after fine pulverization, impurities may be removed by amethod, such as filtration, ultrafiltration, and dialysis, followed bypurification with a cation-exchange resin, an anion-exchange resin, achelate resin, or the like.

Note that a total content of the components (A) and (B) is preferably0.05 to 5.0 mass % in the conductive polymer compound composition. Whenthe total content of the components (A) and (B) is 0.05 mass % or more,sufficient conductivity or hole injection function is obtained. When thetotal content is 5.0 mass % or less, uniform conductive coating film iseasily obtained.

Examples of the organic solvent, which can be added to the aqueoussolution for the polymerization reaction or can dilute the monomer,include methanol, ethyl acetate, cyclohexanone, methyl amyl ketone,butanediol monomethyl ether, propylene glycol monomethyl ether, ethyleneglycol monomethyl ether, butanediol monoethyl ether, propylene glycolmonoethyl ether, ethylene glycol monoethyl ether, propylene glycoldimethyl ether, diethylene glycol dimethyl ether, propylene glycolmonomethyl ether acetate, propylene glycol monoethyl ether acetate,ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl3-ethoxypropionate, tert-butyl acetate, t-butyl propionate, propyleneglycol mono-t-butyl ether acetate, γ-butyrolactone, mixtures thereof,etc.

Note that the amount of the organic solvent to be used is preferably 0to 1,000 mL based on 1 mol of the monomer, particularly preferably 0 to500 mL. With 1,000 mL or less of the organic solvent, the reactionvessel does not become too large so that it is economical.

[(C) Component: Water-Soluble Organic Solvent]

In the present invention, a water-soluble organic solvent is added toimprove the printability to a material to be processed, such as asubstrate. Examples of such an organic solvent include organic solventsthat are soluble in H₂O and have a boiling point of 250° C. or less atnormal pressure.

Examples thereof include alcohols, such as methanol, ethanol, propanol,and butanol; polyhydric aliphatic alcohols, such as ethylene glycol,propylene glycol, 1,3-propanediol, diethylene glycol, dipropyleneglycol, 1,3-butylene glycol, 1,4-butylene glycol, isoprene glycol,1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol,1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, andneopentyl glycol; linear ethers, such as dialkyl ether, dimethoxyethane,ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether,propylene glycol monoalkyl ether, propylene glycol dialkyl ether,butanediol monoalkyl ether, polyethylene glycol dialkyl ether, andpolypropylene glycol dialkyl ether; cyclic ether compounds, such asdioxane and tetrahydrofuran; polar solvents, such as cyclohexanone,methyl amyl ketone, ethyl acetate, diethylene glycol dimethyl ether,propylene glycol monomethyl ether acetate, propylene glycol monoethylether acetate, ethyl pyruvate, butyl acetate, methyl3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate,t-butyl propionate, propylene glycol mono-t-butyl ether acetate,γ-butyrolactone, N-methyl-2-pyrrolidone, N,N′-dimethylformamide,N,N′-dimethylacetamide, dimethylsulfoxide, and hexamethylenephosphotriamide; carbonate compounds, such as ethylene carbonate andpropylene carbonate; heterocyclic compounds, such as3-methyl-2-oxazolidinone; nitrile compounds, such as acetonitrile,glutaronitrile, methoxyacetonitrile, propionitrile, and benzonitrile;mixtures thereof; etc.

The organic solvent (C) to be mixed with a H₂O dispersion of thecomposite of (A) and (B) is essentially a water-soluble organic solvent.The organic solvent (C) may include an organic solvent (C1) having aboiling point of 120° C. or more, and an organic solvent (C2) having aboiling point of less than 120° C. It is possible to use, for example,either (C1) or (C2) singly, or a mixture of (C1) and (C2). Thecontent(s) preferably satisfy 1.0 wt %≤(C1)+(C2)≤50.0 wt %, morepreferably 5.0 wt %≤(C1)+(C2)≤30.0 wt %, relative to a total of thecomponents (A), (B), and (D).

Further, the components (C1) and (C2) are preferably selected fromalcohols, ethers, esters, ketones, and nitriles each of which has 1 to 7carbon atoms.

Additionally, the use of an organic solvent having a boiling pointhigher than that of H₂O in the water-soluble organic solvent makes itpossible to avoid solid content precipitation around a nozzle and solidcontent precipitation due to drying between ejection of the liquidmaterial from a nozzle tip and landing on a substrate.

[(D) Component: H₂O]

In the inventive composition, the composite of the components (A) and(B) is dispersed in H₂O as a component (D), and the inventivecomposition contains a water-soluble organic solvent (C). As thecomponent (D), for example, ultrapure water can be used.

[(E) Component]

To the composition in which the H₂O dispersion of the composite of thecomponents (A) and (B) is mixed with the organic solvent (C), a compound(E) shown by the following general formula (3) can be further added.

In the formula, R²⁰¹ and R²⁰² each independently represent any of ahydrogen atom, a heteroatom, and a linear, branched, or cyclicmonovalent hydrocarbon group having 1 to 20 carbon atoms optionallyhaving a heteroatom. R²⁰³ and R²⁰⁴ each independently represent any of ahydrogen atom and a linear, branched, or cyclic monovalent hydrocarbongroup having 1 to 20 carbon atoms optionally having a heteroatom. R²⁰¹and R²⁰³, or R²⁰¹ and R²⁰⁴, are optionally bonded to each other to forma ring. L represents a linear, branched, or cyclic tetravalent organicgroup having 1 to 20 carbon atoms optionally having a heteroatom. When Lhas a heteroatom, the heteroatom may be an ion.

As a result of incorporating the component (E), when the conductivepolymer composition is used to form a film as an electrode or holeinjection layer of a thin film-stacked device, such as organic EL andsolar cell, the influence of acid can be relieved by suppressing theacid diffusion into an adjacent layer and other constituent layers ofthe laminate structure. Moreover, when the inventive conductive polymercomposition contains the component (E) and this conductive polymercomposition is used to form a film as a constituent of a thin-filmdevice having a laminate structure on a material to be processed, theacid diffusion into an adjacent layer and other constituent layers ofthe laminate-structure device is further suppressed. Thus, the acidinfluence can be further relieved.

In the present invention, only one kind of the compound (E) shown by thegeneral formula (3) may be used, or two or more kinds thereof may beused in mixture. Moreover, any known compound can be used.

The structure of the compound shown by the general formula (3) can bespecifically exemplified by the following.

More preferably, the inventive conductive polymer composition containsthe compound shown by the general formula (3), in which L represents alinear, branched or cyclic tetravalent organic group having 2 to 10carbon atoms optionally having a heteroatom.

Other than the structures shown by the general formula (3), compoundsshown in the following formula (7) can also be suitably used in thepresent invention.

Additionally, in the inventive conductive polymer composition, thecompound shown by the general formula (3) and the compound(s) shown bythe formula (7) are preferably in an amount of 1 part by mass to 50parts by mass, further more preferably 5 parts by mass to 30 parts bymass, based on 100 parts by mass of the composite of the components (A)and (B). When the compound shown by the general formula (3) and thecompound(s) shown by the formula (7) are contained in such amounts, the1-1+ diffusion from a film formed of the inventive conductive polymercomposition to an adjacent layer can be controlled.

[Other Components] (Surfactant)

In the present invention, a surfactant may be added to further increasewettability to a material to be processed, such as a substrate. Examplesof such a surfactant include various surfactants such as nonionic,cationic, and anionic surfactants. Specific examples thereof includenonionic surfactants, such as polyoxyethylene alkyl ether,polyoxyethylene alkylphenyl ether, polyoxyethylene carboxylic acidester, sorbitan ester, and polyoxyethylene sorbitan ester; cationicsurfactants, such as alkyltrimethyl ammonium chloride and alkylbenzylammonium chloride; anionic surfactants, such as alkyl or alkylallylsulfates, alkyl or alkylallyl sulfonate, and dialkyl sulfosuccinate;amphoteric ionic surfactants, such as amino acid type and betaine type;etc.

Preferably, a nonionic surfactant is contained in an amount of 1 part bymass to 15 parts by mass based on 100 parts by mass of the composite ofthe components (A) and (B).

As has been described above, the inventive conductive polymercomposition is capable of efficiently removing residual moisture in thefilm during the film formation, has favorable filterability and highcontinuous-film formability on inorganic and organic substrates evenwhen a spray coater or inkjet printer is used, and is also capable offorming a conductive film having favorable flatness and hightransparency.

[Substrate]

The present invention provides a substrate having an organic EL device,the organic EL device including a hole injection layer formed from theabove-described conductive polymer composition.

In addition, the substrate of the present invention can be producedaccording to a process including a step of applying the above-describedconductive polymer composition by using a spray coater or inkjetprinting.

Examples of the substrate include inorganic substrates, such as glasssubstrate, quartz substrate, photomask blank substrate, silicon wafer,gallium arsenide wafer, and indium phosphide wafer; organic resinsubstrates, such as polyimide, polyethylene terephthalate,polycarbonate, cycloolefin polymer, and triacetyl cellulose; etc.

As described above, according to the present invention, thewater-soluble organic solvent (C) is mixed with the H₂O dispersion ofthe composite composed of (A) the π-conjugated polymer and (B)containing a highly strongly acidic sulfo group and a non-dopingfluorinated unit. This enables low viscosity, favorable filterability,and high formability of continuous film on inorganic and organicsubstrates even when a spray coater or an inkjet printer is employed.Moreover, it is possible to form a conductive film having suitabletransparency, flatness, durability, and conductivity. Further, torelieve the diffusion of H⁺ derived from the acid unit in a non-dopingstate, adding the component (E) makes it possible to suppress the H⁺diffusion to an adjacent layer after the film formation while keepingappropriate acidity as a composition. Such a conductive polymercomposition can function as a hole injection layer.

Example

Hereinafter, the present invention will be specifically described withreference to Examples, but the present invention is not limited thereto.

[Synthesis Examples of Dopant Polymers]

Raw-material monomers employed in polymerizations for copolymerizeddopant polymers represented by (B) in composites used in Examples areshown below.

Synthesis Example 1

Under nitrogen atmosphere, a solution was added dropwise over 4 hours to10 g of methanol stirred at 64° C., the solution containing 1.20 g ofMonomer a″1, 3.75 g of Monomer b″1, and 0.12 g of dimethyl2,2′-azobis(isobutyrate) dissolved in 3 g of methanol. The mixture wasfurther stirred at 64° C. for 4 hours. After cooled to room temperature,the mixture was added dropwise to 10 g of ethyl acetate under vigorousstirring. The resulting solid product was collected by filtration, anddried under vacuum at 50° C. for 15 hours. Thus, a white polymer wasobtained.

The obtained white polymer was dissolved in 100 g of pure water, and theammonium salt was changed to a sulfo group by using an ion exchangeresin. When the obtained polymer was measured by ¹⁹F, ¹H-NMR and GPC,the following analytical results were obtained.

-   -   Weight-average molecular weight (Mw)=21,000    -   Molecular weight distribution (Mw/Mn)=1.90

This polymer compound is designated as (Polymer 1).

Synthesis Example 2

Under nitrogen atmosphere, a solution was added dropwise over 4 hours to10 g of methanol stirred at 64° C., the solution containing 0.6 g ofMonomer a″1, 5.00 g of Monomer b″1, and 0.12 g of dimethyl2,2′-azobis(isobutyrate) dissolved in 3 g of methanol. The mixture wasfurther stirred at 64° C. for 4 hours. After cooled to room temperature,the mixture was added dropwise to 10 g of ethyl acetate under vigorousstirring. The resulting solid product was collected by filtration, anddried under vacuum at 50° C. for 15 hours. Thus, a white polymer wasobtained.

The obtained white polymer was dissolved in 100 g of pure water, and theammonium salt was changed to a sulfo group by using an ion exchangeresin. When the obtained polymer was measured by ¹⁹F, ¹H-NMR and GPC,the following analytical results were obtained.

-   -   Weight-average molecular weight (Mw)=20,500    -   Molecular weight distribution (Mw/Mn)=1.94

This polymer compound is designated as (Polymer 2).

Synthesis Example 3

Under nitrogen atmosphere, a solution was added dropwise over 4 hours to10 g of methanol stirred at 64° C., the solution containing 1.20 g ofMonomer a″2, 3.75 g of Monomer b″1, and 0.12 g of dimethyl2,2′-azobis(isobutyrate) dissolved in 3 g of methanol. The mixture wasfurther stirred at 64° C. for 4 hours. After cooled to room temperature,the mixture was added dropwise to 10 g of ethyl acetate under vigorousstirring. The resulting solid product was collected by filtration, anddried under vacuum at 50° C. for 15 hours. Thus, a white polymer wasobtained.

The obtained white polymer was dissolved in 100 g of pure water, and theammonium salt was changed to a sulfo group by using an ion exchangeresin. When the obtained polymer was measured by ¹⁹F, ¹H-NMR and GPC,the following analytical results were obtained.

-   -   Weight-average molecular weight (Mw)=20,000    -   Molecular weight distribution (Mw/Mn)=1.88

This polymer compound is designated as (Polymer 3).

Synthesis Example 4

Under nitrogen atmosphere, a solution was added dropwise over 4 hours to10 g of methanol stirred at 64° C., the solution containing 1.51 g ofMonomer a″1, 2.55 g of Monomer b″2, and 0.12 g of dimethyl2,2′-azobis(isobutyrate) dissolved in 3 g of methanol. The mixture wasfurther stirred at 64° C. for 4 hours. After cooled to room temperature,the mixture was added dropwise to 10 g of ethyl acetate under vigorousstirring. The resulting solid product was collected by filtration, anddried under vacuum at 50° C. for 15 hours. Thus, a white polymer wasobtained.

The obtained white polymer was dissolved in 100 g of pure water, and theammonium salt was changed to a sulfo group by using an ion exchangeresin. When the obtained polymer was measured by ¹⁹F, ¹H-NMR and GPC,the following analytical results were obtained.

-   -   Weight-average molecular weight (Mw)=22,000    -   Molecular weight distribution (Mw/Mn)=1.93

This polymer compound is designated as (Polymer 4).

Synthesis Example 5

Under nitrogen atmosphere, a solution was added dropwise over 4 hours to10 g of methanol stirred at 64° C., the solution containing 0.60 g ofMonomer a″1, 4.07 g of Monomer b″2, and 0.12 g of dimethyl2,2′-azobis(isobutyrate) dissolved in 3 g of methanol. The mixture wasfurther stirred at 64° C. for 4 hours. After cooled to room temperature,the mixture was added dropwise to 10 g of ethyl acetate under vigorousstirring. The resulting solid product was collected by filtration, anddried under vacuum at 50° C. for 15 hours. Thus, a white polymer wasobtained.

The obtained white polymer was dissolved in 100 g of pure water, and theammonium salt was changed to a sulfo group by using an ion exchangeresin. When the obtained polymer was measured by ¹⁹F, ¹H-NMR and GPC,the following analytical results were obtained.

-   -   Weight-average molecular weight (Mw)=19,500    -   Molecular weight distribution (Mw/Mn)=1.99

This polymer compound is designated as (Polymer 5).

Synthesis Example 6

Under nitrogen atmosphere, a solution was added dropwise over 4 hours to10 g of methanol stirred at 64° C., the solution containing 1.08 g ofMonomer a″6, 3.75 g of Monomer b″1, and 0.12 g of dimethyl2,2′-azobis(isobutyrate) dissolved in 3 g of methanol. The mixture wasfurther stirred at 64° C. for 4 hours. After cooled to room temperature,the mixture was added dropwise to 10 g of ethyl acetate under vigorousstirring. The resulting solid product was collected by filtration, anddried under vacuum at 50° C. for 15 hours. Thus, a white polymer wasobtained.

The obtained white polymer was dissolved in 100 g of pure water, and theammonium salt was changed to a sulfo group by using an ion exchangeresin. When the obtained polymer was measured by ¹⁹F, ¹H-NMR and GPC,the following analytical results were obtained.

-   -   Weight-average molecular weight (Mw)=21,500    -   Molecular weight distribution (Mw/Mn)=2.07

This polymer compound is designated as (Polymer 6).

Synthesis Example 7

Under nitrogen atmosphere, a solution was added dropwise over 4 hours to10 g of methanol stirred at 64° C., the solution containing 0.87 g ofMonomer a″7, 5.00 g of Monomer b″1, and 0.12 g of dimethyl2,2′-azobis(isobutyrate) dissolved in 3 g of methanol. The mixture wasfurther stirred at 64° C. for 4 hours. After cooled to room temperature,the mixture was added dropwise to 10 g of ethyl acetate under vigorousstirring. The resulting solid product was collected by filtration, anddried under vacuum at 50° C. for 15 hours. Thus, a white polymer wasobtained.

The obtained white polymer was dissolved in 100 g of pure water, and theammonium salt was changed to a sulfo group by using an ion exchangeresin. When the obtained polymer was measured by ¹⁹F, ¹H-NMR and GPC,the following analytical results were obtained.

-   -   Weight-average molecular weight (Mw)=19,500    -   Molecular weight distribution (Mw/Mn)=2.00

This polymer compound is designated as (Polymer 7).

Synthesis Example 8

Under nitrogen atmosphere, a solution was added dropwise over 4 hours to10 g of methanol stirred at 64° C., the solution containing 1.00 g ofMonomer a″8, 5.00 g of Monomer b″1, and 0.12 g of dimethyl2,2′-azobis(isobutyrate) dissolved in 3 g of methanol. The mixture wasfurther stirred at 64° C. for 4 hours. After cooled to room temperature,the mixture was added dropwise to 10 g of ethyl acetate under vigorousstirring. The resulting solid product was collected by filtration, anddried under vacuum at 50° C. for 15 hours. Thus, a white polymer wasobtained.

The obtained white polymer was dissolved in 100 g of pure water, and theammonium salt was changed to a sulfo group by using an ion exchangeresin. When the obtained polymer was measured by ¹⁹F, ¹H-NMR and GPC,the following analytical results were obtained.

-   -   Weight-average molecular weight (Mw)=20,000    -   Molecular weight distribution (Mw/Mn)=1.85

This polymer compound is designated as (Polymer 8).

Synthesis Example 9

Under nitrogen atmosphere, a solution was added dropwise over 4 hours to10 g of methanol stirred at 64° C., the solution containing 0.90 g ofMonomer a″1, 4.60 g of Monomer b″5, and 0.12 g of dimethyl2,2′-azobis(isobutyrate) dissolved in 3 g of methanol. The mixture wasfurther stirred at 64° C. for 4 hours. After cooled to room temperature,the mixture was added dropwise to 10 g of ethyl acetate under vigorousstirring. The resulting solid product was collected by filtration, anddried under vacuum at 50° C. for 15 hours. Thus, a white polymer wasobtained.

The obtained white polymer was dissolved in 100 g of pure water, and theammonium salt was changed to a sulfo group by using an ion exchangeresin. When the obtained polymer was measured by ¹⁹F, ¹H-NMR and GPC,the following analytical results were obtained.

-   -   Weight-average molecular weight (Mw)=26,000    -   Molecular weight distribution (Mw/Mn)=2.04

This polymer compound is designated as (Polymer 9).

Synthesis Example 10

Under nitrogen atmosphere, a solution was added dropwise over 4 hours to10 g of methanol stirred at 64° C., the solution containing 0.90 g ofMonomer a″1, 2.35 g of Monomer b″6, and 0.12 g of dimethyl2,2′-azobis(isobutyrate) dissolved in 3 g of methanol. The mixture wasfurther stirred at 64° C. for 4 hours. After cooled to room temperature,the mixture was added dropwise to 10 g of ethyl acetate under vigorousstirring. The resulting solid product was collected by filtration, anddried under vacuum at 50° C. for 15 hours. Thus, a white polymer wasobtained.

The obtained white polymer was dissolved in 100 g of pure water, and thesodium salt was changed to a sulfo group by using an ion exchange resin.When the obtained polymer was measured by ¹⁹F, ¹H-NMR and GPC, thefollowing analytical results were obtained.

-   -   Weight-average molecular weight (Mw)=31,000    -   Molecular weight distribution (Mw/Mn)=2.11

This polymer compound is designated as (Polymer 10).

[Preparation of Conductive Polymer Composite Dispersion containingPolythiophene as π-Conjugated Polymer]

Preparation Example 1

2.27 g of 3,4-ethylenedioxythiophene and a solution in which 15.0 g ofDopant Polymer 1 had been dissolved in 1,000 mL of ultrapure water weremixed at 30° C.

The obtained mixture solution was maintained at 30° C. under stirring.In this state, 4.99 g of sodium persulfate dissolved in 100 mL ofultrapure water and an oxidizing catalyst solution of 1.36 g of ferricsulfate were gradually added thereto and stirred for 4 hours to reactthese materials.

To the obtained reaction solution, 1,000 mL of ultrapure water wasadded, and about 1,000 mL of the solution was removed by using theultrafiltration method. This operation was repeated three times.

Then, to the processed solution after the filtration treatment, 200 mLof sulfuric acid diluted to 10 mass % and 2,000 mL of ion exchangedwater were added. About 2,000 mL of the processed solution was removedby using the ultrafiltration method, and 2,000 mL of ion exchanged waterwas added thereto. About 2,000 mL of the solution was removed by usingthe ultrafiltration method. This operation was repeated three times.

Further, 2,000 mL of ion exchanged water was added to the obtainedprocessed solution, and about 2,000 mL of the processed solution wasremoved by using the ultrafiltration method. This operation was repeatedfive times. The resultant was concentrated to obtain 2.5 mass % ofblue-colored Conductive Polymer Composite Dispersion 1.

The ultrafiltration conditions were as follows.

-   -   Molecular weight cutoff of ultrafiltration membrane: 30 K    -   Cross flow type    -   Flow amount of supplied liquid: 3,000 mL/minute    -   Membrane partial pressure: 0.12 Pa    -   Note that the ultrafiltration was carried out under the same        conditions in the other Preparation Examples.

Preparation Example 2

Preparation was carried out in the same manner as in Preparation Example1 except for changing 15.0 g of Dopant Polymer 1 to Dopant Polymer 2,and changing the amount of 3,4-ethylenedioxythiophene blended to 2.09 g,the amount of sodium persulfate blended to 4.59 g, and the amount offerric sulfate blended to 1.25 g. Thus, Conductive Polymer CompositeDispersion 2 was obtained.

Preparation Example 3

Preparation was carried out in the same manner as in Preparation Example1 except for changing 15.0 g of Dopant Polymer 1 to Dopant Polymer 3,and changing the amount of 3,4-ethylenedioxythiophene blended to 2.27 g,the amount of sodium persulfate blended to 4.99 g, and the amount offerric sulfate blended to 1.36 g. Thus, Conductive Polymer CompositeDispersion 3 was obtained.

Preparation Example 4

Preparation was carried out in the same manner as in Preparation Example1 except for changing 15.0 g of Dopant Polymer 1 to Dopant Polymer 4,and changing the amount of 3,4-ethylenedioxythiophene blended to 2.79 g,the amount of sodium persulfate blended to 6.13 g, and the amount offerric sulfate blended to 1.67 g. Thus, Conductive Polymer CompositeDispersion 4 was obtained.

Preparation Example 5

Preparation was carried out in the same manner as in Preparation Example1 except for changing 15.0 g of Dopant Polymer 1 to Dopant Polymer 5,and changing the amount of 3,4-ethylenedioxythiophene blended to 2.64 g,the amount of sodium persulfate blended to 5.82 g, and the amount offerric sulfate blended to 1.59 g. Thus, Conductive Polymer CompositeDispersion 5 was obtained.

Preparation Example 6

Preparation was carried out in the same manner as in Preparation Example1 except for changing 15.0 g of Dopant Polymer 1 to Dopant Polymer 6,and changing the amount of 3,4-ethylenedioxythiophene blended to 2.34 g,the amount of sodium persulfate blended to 5.14 g, and the amount offerric sulfate blended to 1.40 g. Thus, Conductive Polymer CompositeDispersion 6 was obtained.

Preparation Example 7

Preparation was carried out in the same manner as in Preparation Example1 except for changing 15.0 g of Dopant Polymer 1 to Dopant Polymer 7,and changing the amount of 3,4-ethylenedioxythiophene blended to 1.97 g,the amount of sodium persulfate blended to 4.32 g, and the amount offerric sulfate blended to 1.17 g. Thus, Conductive Polymer CompositeDispersion 7 was obtained.

Preparation Example 8

Preparation was carried out in the same manner as in Preparation Example1 except for changing 15.0 g of Dopant Polymer 1 to Dopant Polymer 8,and changing the amount of 3,4-ethylenedioxythiophene blended to 1.91 g,the amount of sodium persulfate blended to 4.20 g, and the amount offerric sulfate blended to 1.12 g. Thus, Conductive Polymer CompositeDispersion 8 was obtained.

Preparation Example 9

Preparation was carried out in the same manner as in Preparation Example1 except for changing 15.0 g of Dopant Polymer 1 to Dopant Polymer 9,and changing the amount of 3,4-ethylenedioxythiophene blended to 2.06 g,the amount of sodium persulfate blended to 4.54 g, and the amount offerric sulfate blended to 1.24 g. Thus, Conductive Polymer CompositeDispersion 9 was obtained.

Preparation Example 10

Preparation was carried out in the same manner as in Preparation Example1 except for changing 15.0 g of Dopant Polymer 1 to Dopant Polymer 10,and changing the amount of 3,4-ethylenedioxythiophene blended to 2.97 g,the amount of sodium persulfate blended to 6.53 g, and the amount offerric sulfate blended to 1.78 g. Thus, Conductive Polymer CompositeDispersion 10 was obtained.

[Evaluation of Conductive Polymer Composition Containing Polythiopheneas π-Conjugated Polymer] Examples

2.5 mass % of one of the conductive polymer composite dispersionsobtained in Preparation Examples 1 to 10 was mixed with 10 wt % of PGMEA(propylene glycol monomethyl ether acetate) as the organic solvent (C1)and 5 wt % of EtOH as the organic solvent (C2). The mixtures obtained inthis manner were respectively designated as Examples 1 to 10.

2.5 mass % of one of the conductive polymer composite dispersionsobtained in Preparation Examples 1 to 10 was mixed with 10 wt % of PGMEA(propylene glycol monomethyl ether acetate) as the organic solvent (C1)and 5 wt % of IPA (2-propanol) as the organic solvent (C2). The mixturesobtained in this manner were respectively designated as Examples 11 to20.

2.5 mass % of one of the conductive polymer composite dispersionsobtained in Preparation Examples 1 to 10 was mixed with 10 wt % of PGMEA(propylene glycol monomethyl ether acetate) as the organic solvent (C1)and 5 wt % of ^(t)BuOH (tertiary butyl alcohol) as the organic solvent(C2). The mixtures obtained in this manner were respectively designatedas Examples 21 to 30.

2.5 mass % of one of the conductive polymer composite dispersionsobtained in Preparation Examples 1 to 10 was mixed with 15 wt % of PGMEA(propylene glycol monomethyl ether acetate) as the organic solvent (C1)and 5 wt % of EtOH as the organic solvent (C2). The mixtures obtained inthis manner were respectively designated as Examples 31 to 40.

2.5 mass % of one of the conductive polymer composite dispersionsobtained in Preparation Examples 1 to 10 was mixed with 15 wt % of PGMEA(propylene glycol monomethyl ether acetate) as the organic solvent (C1)and 5 wt % of IPA (2-propanol) as the organic solvent (C2). The mixturesobtained in this manner were respectively designated as Examples 41 to50.

2.5 mass % of one of the conductive polymer composite dispersionsobtained in Preparation Examples 1 to 10 was mixed with 15 wt % of PGMEA(propylene glycol monomethyl ether acetate) as the organic solvent (C1)and 5 wt % of ^(t)BuOH (tertiary butyl alcohol) as the organic solvent(C2). The mixtures obtained in this manner were respectively designatedas Examples 51 to 60.

2.5 mass % of one of the conductive polymer composite dispersionsobtained in Preparation Examples 1 to 10 was mixed with 10 wt % of PGME(propylene glycol monomethyl ether) as the organic solvent (C1) and 5 wt% of EtOH as the organic solvent (C2). The mixtures obtained in thismanner were respectively designated as Examples 61 to 70.

2.5 mass % of one of the conductive polymer composite dispersionsobtained in Preparation Examples 1 to 10 was mixed with 10 wt % of PGME(propylene glycol monomethyl ether) as the organic solvent (C1) and 5 wt% of IPA (2-propanol) as the organic solvent (C2). The mixtures obtainedin this manner were respectively designated as Examples 71 to 80.

2.5 mass % of one of the conductive polymer composite dispersionsobtained in Preparation Examples 1 to 10 was mixed with 10 wt % of PGME(propylene glycol monomethyl ether) as the organic solvent (C1) and 5 wt% of ^(t)BuOH (tertiary butyl alcohol) as the organic solvent (C2). Themixtures obtained in this manner were respectively designated asExamples 81 to 90.

2.5 mass % of one of the conductive polymer composite dispersionsobtained in Preparation Examples 1 to 10 was mixed with 15 wt % of PGME(propylene glycol monomethyl ether) as the organic solvent (C1) and 5 wt% of EtOH as the organic solvent (C2). The mixtures obtained in thismanner were respectively designated as Examples 91 to 100.

2.5 mass % of one of the conductive polymer composite dispersionsobtained in Preparation Examples 1 to 10 was mixed with 15 wt % of PGME(propylene glycol monomethyl ether) as the organic solvent (C1) and 5 wt% of IPA (2-propanol) as the organic solvent (C2). The mixtures obtainedin this manner were respectively designated as Examples 101 to 110.

2.5 mass % of one of the conductive polymer composite dispersionsobtained in Preparation Examples 1 to 10 was mixed with 15 wt % of PGME(propylene glycol monomethyl ether) as the organic solvent (C1) and 5 wt% of ^(t)BuOH (tertiary butyl alcohol) as the organic solvent (C2). Themixtures obtained in this manner were respectively designated asExamples 111 to 120.

One of the compositions of Examples 1 to 120 was mixed with 0.43 mass %of L-(+)-Lysine included in the compound (E) shown by the generalformula (3) and a fluoroalkyl-based nonionic surfactant FS-31 (availablefrom DuPont). Then, such mixtures were filtered using cellulose filters(manufactured by ADVANTEC Corporation) having a pore size of 3.00 to0.45 μm. In this manner, conductive polymer compositions were preparedand respectively designated as Composition Examples 121 to 240.

COMPARATIVE EXAMPLES

2.5 mass % of the conductive polymer composite dispersions obtained inPreparation Examples 1 to 10 were respectively designated as ComparativeExamples 1 to 10.

2.5 mass % of one of the conductive polymer compound dispersionsobtained in Preparation Examples 1 to 10 was mixed with 0.43 mass % ofL-(+)-Lysine included in the compound (E) shown by the general formula(3) and a fluoroalkyl-based nonionic surfactant FS-31 (available fromDuPont). The mixtures obtained in this manner were respectivelydesignated as Comparative Examples 11 to 20.

The conductive polymer compositions of Examples and Comparative Examplesprepared as described above were evaluated as follows.

(Filterability)

In the preparations of the conductive polymer composite compositions ofExamples and Comparative Examples, the filtration was carried out usingregenerated cellulose filters having pore sizes of 3.0 to 0.20 μm. Inthis event, the pore size limits of the filters through which thecompositions were successfully filtered and passed are shown in Tables1-1 to 1-9.

(Surface Tension)

The surface tension of each composition was measured using a du Nouysurface tensiometer Model D (manufactured by Ito Seisakusho Co., Ltd.).Tables 1-1 to 1-9 show the result.

(Viscosity)

The liquid temperature of each conductive polymer composition wasadjusted to 25° C. Then, 35 mL of each composition was weighed into ameasurement cell specifically attached to a tuning fork vibration typeviscometer SV-10 (manufactured by A&D Company Limited) to measure theviscosity immediately after the preparation. Tables 1-1 to 1-9 show theresult.

(pH Measurement)

The pH of each conductive polymer composition was measured using a pHmeter D-52 (manufactured by HORIBA, Ltd.). Tables 1-1 to 1-9 show theresult.

(Transmittance)

From the refractive index (n, k) at a wavelength of 636 nm measuredusing a spectroscopic ellipsometer (VASE) with variable incident angle,the transmittance for light beam with a wavelength of 550 nm at FT=200nm was calculated. Tables 1-1 to 1-9 show the result.

(Conductivity)

Onto a SiO₂ wafer having a diameter of 4 inches (100 mm), 1.0 mL of aconductive polymer composition was added dropwise. After 10 seconds, thewhole wafer was spin-coated therewith by using a spinner. Thespin-coating conditions were so adjusted that the film thickness became100±5 nm. Baking was carried out in a precise constant temperature ovenat 120° C. for 30 minutes to remove the solvent. Thus, a conductive filmwas obtained.

The electric conductivity (S/cm) of the obtained conductive film wasdetermined from the actually measured value of the film thickness andthe surface resistivity (Ω/□) measured by using Hiresta-UP MCP-HT450 andLoresta-GP MCP-T610 (both manufactured by Mitsubishi ChemicalCorporation). Tables 1-1 to 1-9 show the result.

(Spray Coater Film Formability)

A 35 mm-square non-alkaline glass substrate was subjected to surfacecleaning with UV/03 for 10 minutes, and coated with one of theconductive polymer compositions by using a spray coater NVD203(manufactured by Fujimori Technical Laboratory Inc.) to form a film. Thecoating film surface was observed with an optical microscope and aninterference microscope to evaluate whether a continuous film was formedor not. Tables 1-1 to 1-9 show the result.

TABLE 1-1 Filter- ability (filter pore size Surface Transmittance limitfor tension Viscosity (FT = 200 nm, Conductivity passage) (mN/m) (mPa/S)pH λ = 550 nm) (S/cm) Spray-coated film state Example 1 0.20 μm 37.02.80 3.2 98% 1.53E+00 continuous film (flat) Example 2 0.20 μm 36.0 3.003.1 95% 2.33E+00 continuous film (flat) Example 3 0.20 μm 36.5 2.98 3.096% 5.55E+00 continuous film (flat) Example 4 0.20 μm 37.0 2.79 3.5 94%3.00E+00 continuous film (flat) Example 5 0.20 μm 36.2 2.88 3.6 95%6.60E+00 continuous film (flat) Example 6 0.20 μm 36.8 2.86 3.5 96%4.25E+00 continuous film (flat) Example 7 0.20 μm 37.5 2.69 3.1 98%3.36E+00 continuous film (flat) Example 8 0.20 μm 36.6 2.78 3.8 98%3.41E+00 continuous film (flat) Example 9 0.20 μm 37.8 2.89 3.5 99%2.00E+00 continuous film (flat) Example 10 0.20 μm 38.0 2.99 3.6 97%9.53E−01 continuous film (flat) Example 11 0.20 μm 37.9 2.75 2.9 95%3.33E+00 continuous film (flat) Example 12 0.20 μm 36.8 2.68 2.5 94%4.56E+00 continuous film (flat) Example 13 0.20 μm 38.5 2.89 3.5 95%2.36E+00 continuous film (flat) Example 14 0.20 μm 38.0 3.00 3.1 96%5.69E+00 continuous film (flat) Example 15 0.20 μm 37.1 2.77 3.0 96%6.22E+00 continuous film (flat) Example 16 0.20 μm 37.7 2.96 2.9 96%2.78E+00 continuous film (flat) Example 17 0.20 μm 38.1 2.89 3.4 97%4.96E+00 continuous film (flat) Example 18 0.20 μm 38.0 2.87 3.4 95%6.33E+00 continuous film (flat) Example 19 0.20 μm 36.9 2.69 3.5 97%2.58E+00 continuous film (flat) Example 20 0.20 μm 37.5 2.87 3.0 98%5.69E+00 continuous film (flat) Example 21 0.20 μm 37.4 2.69 3.3 95%4.15E+00 continuous film (flat) Example 22 0.20 μm 37.7 2.86 3.5 94%6.14E+00 continuous film (flat) Example 23 0.20 μm 38.2 2.87 3.4 95%7.53E+00 continuous film (flat) Example 24 0.20 μm 36.9 2.99 3.9 96%4.65E+00 continuous film (flat) Example 25 0.20 μm 37.7 2.94 3.5 93%9.60E−01 continuous film (flat) Example 26 0.20 μm 37.1 2.86 2.5 95%5.60E+00 continuous film (flat) Example 27 0.20 μm 37.5 2.92 3.4 95%4.90E+00 continuous film (flat) Example 28 0.20 μm 37.9 3.00 3.4 92%5.60E+00 continuous film (flat) Example 29 0.20 μm 38.2 2.79 2.8 98%5.70E+00 continuous film (flat) Example 30 0.20 μm 38.0 3.12 3.9 95%3.60E+00 continuous film (flat)

TABLE 1-2 Filter- ability (filter pore size Surface Transmittance limitfor tension Viscosity (FT = 200 nm, Conductivity passage) (mN/m) (mPa/S)pH λ = 550 nm) (S/cm) Spray-coated film state Example 31 0.20 μm 37.02.95 3.4 96% 2.50E+00 continuous film (flat) Example 32 0.20 μm 37.62.86 3.3 94% 6.70E+00 continuous film (flat) Example 33 0.20 μm 37.52.82 3.0 95% 8.90E+00 continuous film (flat) Example 34 0.20 μm 37.92.70 3.6 96% 5.10E+00 continuous film (flat) Example 35 0.20 μm 38.02.69 2.9 96% 2.70E+00 continuous film (flat) Example 36 0.20 μm 37.42.89 3.4 95% 4.00E+00 continuous film (flat) Example 37 0.20 μm 37.72.93 3.6 92% 3.90E+00 continuous film (flat) Example 38 0.20 μm 38.03.02 3.6 93% 6.60E+00 continuous film (flat) Example 39 0.20 μm 37.62.86 3.5 94% 3.70E+00 continuous film (flat) Example 40 0.20 μm 37.82.79 3.6 99% 4.90E+00 continuous film (flat) Example 41 0.20 μm 36.02.83 3.3 95% 4.50E+00 continuous film (flat) Example 42 0.20 μm 36.92.81 3.7 96% 6.10E+00 continuous film (flat) Example 43 0.20 μm 37.02.59 3.6 94% 3.80E+00 continuous film (flat) Example 44 0.20 μm 36.52.93 3.1 92% 4.90E+00 continuous film (flat) Example 45 0.20 μm 38.02.82 3.8 96% 6.00E+00 continuous film (flat) Example 46 0.20 μm 38.53.10 3.2 97% 2.90E+00 continuous film (flat) Example 47 0.20 μm 37.72.59 3.8 96% 6.80E+00 continuous film (flat) Example 48 0.20 μm 36.92.89 2.6 95% 5.69E+00 continuous film (flat) Example 49 0.20 μm 37.22.96 3.4 95% 6.33E+00 continuous film (flat) Example 50 0.20 μm 37.82.73 3.6 94% 4.26E+00 continuous film (flat) Example 51 0.20 μm 38.22.75 3.7 92% 3.95E+00 continuous film (flat) Example 52 0.20 μm 38.02.91 3.6 95% 6.00E+00 continuous film (flat) Example 53 0.20 μm 37.42.85 3.6 93% 7.35E+00 continuous film (flat) Example 54 0.20 μm 37.72.69 3.5 95% 6.37E+00 continuous film (flat) Example 55 0.20 μm 37.52.80 3.0 95% 5.00E+00 continuous film (flat) Example 56 0.20 μm 37.62.82 3.2 97% 4.29E+00 continuous film (flat) Example 57 0.20 μm 38.02.96 3.2 99% 6.23E+00 continuous film (flat) Example 58 0.20 μm 37.03.03 3.8 93% 4.23E+00 continuous film (flat) Example 59 0.20 μm 36.82.86 2.5 92% 6.37E+03 continuous film (flat) Example 60 0.20 μm 37.52.91 3.0 96% 4.69E+00 continuous film (flat)

TABLE 1-3 Filter- ability (filter pore size Surface Transmittance limitfor tension Viscosity (FT = 200 nm, Conductivity passage) (mN/m) (mPa/S)pH λ = 550 nm) (S/cm) Spray-coated film state Example 61 0.20 μm 36.52.86 2.9 94% 7.59E+00 continuous film (flat) Example 62 0.20 μm 37.72.79 3.6 93% 3.68E+00 continuous film (flat) Example 63 0.20 μm 37.22.69 3.0 96% 5.96E+00 continuous film (flat) Example 64 0.20 μm 36.72.85 3.5 96% 4.69E+00 continuous film (flat) Example 65 0.20 μm 37.12.82 3.0 95% 5.37E+03 continuous film (flat) Example 66 0.20 μm 38.52.95 3.9 95% 2.99E+00 continuous film (flat) Example 67 0.20 μm 37.02.90 3.2 95% 7.89E+00 continuous film (flat) Example 68 0.20 μm 38.62.58 3.4 95% 8.00E+00 continuous film (flat) Example 69 0.20 μm 38.22.67 3.4 96% 8.88E+00 continuous film (flat) Example 70 0.20 μm 37.53.09 3.9 95% 5.69E+00 continuous film (flat) Example 71 0.20 μm 37.42.85 3.5 94% 6.27E+00 continuous film (flat) Example 72 0.20 μm 36.52.76 3.1 98% 4.95E+00 continuous film (flat) Example 73 0.20 μm 37.02.81 3.0 96% 5.56E+00 continuous film (flat) Example 74 0.20 μm 36.82.80 3.6 97% 6.75E+00 continuous film (flat) Example 75 0.20 μm 35.92.86 3.6 95% 2.99E+00 continuous film (flat) Example 76 0.20 μm 37.42.86 3.0 96% 6.77E+00 continuous film (flat) Example 77 0.20 μm 37.52.82 3.5 94% 4.50E+00 continuous film (flat) Example 78 0.20 μm 36.52.91 3.2 96% 4.59E+00 continuous film (flat) Example 79 0.20 μm 38.52.86 3.8 98% 6.78E+00 continuous film (flat) Example 80 0.20 μm 36.42.81 3.3 95% 8.93E+00 continuous film (flat) Example 81 0.20 μm 36.22.91 3.6 96% 5.48E+00 continuous film (flat) Example 82 0.20 μm 38.02.73 3.4 97% 7.58E+00 continuous film (flat) Example 83 0.20 μm 37.52.85 3.7 95% 6.50E+00 continuous film (flat) Example 84 0.20 μm 37.23.01 3.5 95% 4.15E+00 continuous film (flat) Example 85 0.20 μm 37.43.08 3.0 96% 2.68E+00 continuous film (flat) Example 86 0.20 μm 37.72.93 3.2 92% 3.58E+00 continuous film (flat) Example 87 0.20 μm 38.02.78 3.8 94% 5.55E+00 continuous film (flat) Example 88 0.20 μm 38.62.90 3.4 92% 6.30E+00 continuous film (flat) Example 89 0.20 μm 37.42.75 3.5 95% 5.04E+00 continuous film (flat) Example 90 0.20 μm 37.22.81 3.9 95% 8.59E+00 continuous film (flat)

TABLE 1-4 Filter- ability (filter pore size Surface Transmittance limitfor tension Viscosity (FT = 200 nm, Conductivity passage) (mN/m) (mPa/S)pH λ = 550 nm) (S/cm) Spray-coated film state Example 91 0.20 μm 37.42.67 3.6 95% 5.60E+00 continuous film (flat) Example 92 0.20 μm 38.03.12 3.0 97% 5.77E+00 continuous film (flat) Example 93 0.20 μm 37.53.00 3.4 98% 4.80E+00 continuous film (flat) Example 94 0.20 μm 37.02.91 3.5 97% 6.00E+00 continuous film (flat) Example 95 0.20 μm 37.52.76 2.5 96% 2.58E+00 continuous film (flat) Example 96 0.20 μm 36.72.81 3.8 95% 5.69E+00 continuous film (flat) Example 97 0.20 μm 36.52.95 3.6 94% 6.00E+00 continuous film (flat) Example 98 0.20 μm 37.02.76 3.2 95% 4.25E+00 continuous film (flat) Example 99 0.20 μm 37.22.91 3.0 97% 3.38E+00 continuous film (flat) Example 100 0.20 μm 38.02.90 2.7 95% 3.96E+00 continuous film (flat) Example 101 0.20 μm 37.42.95 3.3 97% 8.37E+03 continuous film (flat) Example 102 0.20 μm 37.72.88 3.4 94% 5.78E+00 continuous film (flat) Example 103 0.20 μm 35.92.76 3.9 94% 4.95E+00 continuous film (flat) Example 104 0.20 μm 36.02.80 3.2 96% 6.76E+00 continuous film (flat) Example 105 0.20 μm 36.83.05 3.0 95% 5.00E+00 continuous film (flat) Example 106 0.20 μm 38.02.75 3.5 98% 2.28E+00 continuous film (flat) Example 107 0.20 μm 37.52.69 3.9 94% 4.69E+00 continuous film (flat) Example 108 0.20 μm 36.83.00 3.3 97% 5.69E+00 continuous film (flat) Example 109 0.20 μm 36.92.86 3.4 96% 5.32E+00 continuous film (flat) Example 110 0.20 μm 37.52.75 3.5 95% 7.58E+00 continuous film (flat) Example 111 0.20 μm 37.72.80 3.6 96% 7.77E+00 continuous film (flat) Example 112 0.20 μm 37.52.92 3.7 94% 6.59E+00 continuous film (flat) Example 113 0.20 μm 37.12.95 3.5 96% 3.58E+00 continuous film (flat) Example 114 0.20 μm 36.52.70 2.9 97% 6.58E+00 continuous film (flat) Example 115 0.20 μm 36.02.83 3.0 95% 4.90E+00 continuous film (flat) Example 116 0.20 μm  8.02.85 3.5 98% 8.59E+00 continuous film (flat) Example 117 0.20 μm 37.02.91 3.6 97% 7.10E+00 continuous film (flat) Example 118 0.20 μm 38.22.73 3.4 96% 6.25E+00 continuous film (flat) Example 119 0.20 μm 37.92.85 3.8 95% 4.44E+00 continuous film (flat) Example 120 0.20 μm 38.62.76 3.0 97% 6.00E+00 continuous film (flat)

TABLE 1-5 Filter- ability (filter pore size Surface Transmittance limitfor tension Viscosity (FT = 200 nm, Conductivity passage) (mN/m) (mPa/S)pH λ = 550 nm) (S/cm) Spray-coated film state Example 121 0.20 μm 34.23.54 6.6 95% 6.50E−05 continuous film (flat) Example 122 0.20 μm 35.23.25 6.3 95% 3.20E−05 continuous film (flat) Example 123 0.20 μm 34.33.65 6.5 96% 6.40E−05 continuous film (flat) Example 124 0.20 μm 35.03.55 6.8 94% 4.20E−05 continuous film (flat) Example 125 0.20 μm 34.23.98 6.9 93% 7.80E−05 continuous film (flat) Example 126 0.20 μm 33.33.78 6.3 95% 4.20E−05 continuous film (flat) Example 127 0.20 μm 33.53.89 6.3 96% 3.20E−05 continuous film (flat) Example 128 0.20 μm 34.03.31 6.5 93% 9.50E−04 continuous film (flat) Example 129 0.20 μm 35.03.52 6.2 95% 6.30E−05 continuous film (flat) Example 130 0.20 μm 34.23.65 6.4 96% 3.20E−05 continuous film (flat) Example 131 0.20 μm 33.23.45 6.8 94% 5.20E−05 continuous film (flat) Example 132 0.20 μm 31.23.11 6.8 96% 6.90E−05 continuous film (flat) Example 133 0.20 μm 32.53.27 6.9 98% 4.90E−05 continuous film (flat) Example 134 0.20 μm 33.33.86 6.6 95% 6.50E−05 continuous film (flat) Example 135 0.20 μm 33.53.56 6.6 96% 3.50E−05 continuous film (flat) Example 136 0.20 μm 36.03.64 6.7 96% 5.20E−05 continuous film (flat) Example 137 0.20 μm 34.23.35 6.4 95% 4.30E−05 continuous film (flat) Example 138 0.20 μm 34.03.25 6.9 96% 5.70E−05 continuous film (flat) Example 139 0.20 μm 33.93.59 6.5 94% 5.30E−05 continuous film (flat) Example 140 0.20 μm 35.13.85 6.5 96% 3.60E−05 continuous film (flat) Example 141 0.20 μm 34.93.15 6.6 97% 3.90E−05 continuous film (flat) Example 142 0.20 μm 34.53.43 6.6 95% 1.90E−04 continuous film (flat) Example 143 0.20 μm 34.04.00 6.9 93% 6.90E−05 continuous film (flat) Example 144 0.20 μm 35.04.10 6.6 95% 2.60E−05 continuous film (flat) Example 145 0.20 μm 34.23.55 6.4 96% 1.50E−04 continuous film (flat) Example 146 0.20 μm 34.93.85 6.5 95% 3.60E−05 continuous film (flat) Example 147 0.20 μm 35.23.68 6.5 96% 2.60E−05 continuous film (flat) Example 148 0.20 μm 33.53.63 6.5 93% 1.60E−04 continuous film (flat) Example 149 0.20 μm 34.63.33 6.6 94% 3.60E−05 continuous film (flat) Example 150 0.20 μm 33.23.37 6.3 95% 5.50E−05 continuous film (flat)

TABLE 1-6 Filter- ability (filter pore size Surface Transmittance limitfor tension Viscosity (FT = 200 nm, Conductivity passage) (mN/m) (mPa/S)pH λ = 550 nm) (S/cm) Spray-coated film state Example 151 0.20 μm 34.13.82 6.2 96% 6.90E−05 continuous film (flat) Example 152 0.20 μm 34.03.49 6.5 96% 6.00E−05 continuous film (flat) Example 153 0.20 μm 34.83.62 6.1 96% 4.40E−05 continuous film (flat) Example 154 0.20 μm 34.63.28 6.8 97% 7.70E−05 continuous film (flat) Example 155 0.20 μm 34.53.27 6.4 95% 4.30E−05 continuous film (flat) Example 156 0.20 μm 34.23.00 6.5 94% 4.00E−05 continuous film (flat) Example 157 0.20 μm 35.03.55 6.6 96% 5.29E−05 continuous film (flat) Example 158 0.20 μm 33.53.99 6.6 96% 9.60E−04 continuous film (flat) Example 159 0.20 μm 33.13.20 6.9 95% 1.50E−04 continuous film (flat) Example 160 0.20 μm 34.14.13 6.1 95% 2.60E−05 continuous film (flat) Example 161 0.20 μm 33.93.28 6.1 96% 4.90E−05 continuous film (flat) Example 162 0.20 μm 35.03.96 6.5 95% 3.30E−05 continuous film (flat) Example 163 0.20 μm 34.64.33 6.4 96% 8.50E−05 continuous film (flat) Example 164 0.20 μm 34.43.18 6.7 95% 5.60E−05 continuous film (flat) Example 165 0.20 μm 34.23.66 6.5 95% 1.80E−04 continuous film (flat) Example 166 0.20 μm 35.03.99 6.5 96% 1.50E−04 continuous film (flat) Example 167 0.20 μm 32.13.58 6.1 95% 1.70E−04 continuous film (flat) Example 168 0.20 μm 33.53.78 6.0 95% 3.40E−05 continuous film (flat) Example 169 0.20 μm 36.03.80 6.5 94% 2.60E−05 continuous film (flat) Example 170 0.20 μm 34.63.26 6.7 95% 3.50E−05 continuous film (flat) Example 171 0.20 μm 34.53.38 6.5 94% 4.70E−05 continuous film (flat) Example 172 0.20 μm 34.43.94 6.6 97% 5.90E−05 continuous film (flat) Example 173 0.20 μm 34.43.80 6.2 96% 1.60E−04 continuous film (flat) Example 174 0.20 μm 33.94.26 6.3 96% 7.60E−05 continuous film (flat) Example 175 0.20 μm 33.63.60 6.3 95% 1.70E−04 continuous film (flat) Example 176 0.20 μm 34.03.84 6.5 96% 2.90E−05 continuous film (flat) Example 177 0.20 μm 35.03.19 6.6 94% 1.60E−04 continuous film (flat) Example 178 0.20 μm 34.84.00 6.4 94% 1.50E−04 continuous film (flat) Example 179 0.20 μm 34.43.76 6.5 97% 2.30E−05 continuous film (flat) Example 180 0.20 μm 34.23.88 6.7 96% 3.50E−05 continuous film (flat)

TABLE 1-7 Filter- ability (filter Trans- pore size Surface mittanceConduc- limit for tension Viscosity (FT = 200 nm, tivity passage) (mN/m)(mPa/S) PH λ = 550 nm) (S/cm) Spray-coated film state Example 181 0.20μm 34.5 3.86 6.5 96% 5.70E−05 continuous film (flat) Example 182 0.20 μm34.2 3.93 6.4 96% 8.60E−05 continuous film (flat) Example 183 0.20 μm34.0 3.25 6.7 95% 4.30E−05 continuous film (flat) Example 184 0.20 μm33.5 3.54 6.5 94% 3.50E−05 continuous film (flat) Example 185 0.20 μm35.0 4.05 6.5 93% 6.90E−05 continuous film (flat) Example 186 0.20 μm35.2 3.48 6.1 95% 6.70E−05 continuous film (flat) Example 187 0.20 μm34.4 3.86 6.0 96% 5.80E−05 continuous film (flat) Example 188 0.20 μm34.9 3.48 6.5 95% 4.90E−05 continuous film (flat) Example 189 0.20 μm34.5 3.32 6.0 94% 8.60E−05 continuous film (flat) Example 190 0.20 μm34.7 3.28 6.5 96% 4.90E−05 continuous film (flat) Example 191 0.20 μm34.4 3.69 6.6 96% 5.60E−05 continuous film (flat) Example 192 0.20 μm34.0 3.98 6.2 96% 6.80E−05 continuous film (flat) Example 193 0.20 μm33.5 3.72 6.3 95% 8.60E−05 continuous film (flat) Example 194 0.20 μm33.9 3.49 6.3 96% 4.80E−05 continuous film (flat) Example 195 0.20 μm33.5 3.68 6.5 94% 5.60E−05 continuous film (flat) Example 196 0.20 μm34.0 3.56 6.4 97% 5.60E−05 continuous film (flat) Example 197 0.20 μm34.5 3.35 6.4 95% 4.90E−05 continuous film (flat) Example 198 0.20 μm36.0 3.91 6.5 96% 7.60E−05 continuous film (flat) Example 199 0.20 μm34.0 3.99 6.7 93% 6.00E−05 continuous film (flat) Example 200 0.20 μm33.9 4.20 6.5 95% 4.30E−05 continuous film (flat) Example 201 0.20 μm35.2 3.99 6.8 94% 5.60E−05 continuous film (flat) Example 202 0.20 μm35.6 3.83 6.9 96% 9.60E−05 continuous film (flat) Example 203 0.20 μm34.8 3.58 6.3 97% 4.80E−05 continuous film (flat) Example 204 0.20 μm34.2 3.51 5.9 95% 5.60E−05 continuous film (flat) Example 205 0.20 μm34.0 3.54 6.5 95% 4.80E−05 continuous film (flat) Example 206 0.20 μm35.2 3.89 6.2 94% 6.90E−05 continuous film (flat) Example 207 0.20 μm35.1 3.99 6.4 95% 5.30E−05 continuous film (flat) Example 208 0.20 μm34.4 4.23 6.4 95% 3.60E−05 continuous film (flat) Example 209 0.20 μm34.0 4.50 6.8 94% 3.50E−05 continuous film (flat) Example 210 0.20 μm34.2 3.18 6.9 96% 3.70E−05 continuous film (flat)

TABLE 1-8 Filter- ability (filter Trans- pore size Surface mittanceConduc- limit for tension Viscosity (FT = 200 nm, tivity passage) (mN/m)(mPa/S) PH λ = 550 nm) (S/cm) Spray-coated film state Example 211 0.20μm 33.5 3.58 6.6 96% 5.90E−05 continuous film (flat) Example 212 0.20 μm34.6 3.67 6.6 95% 6.90E−05 continuous film (flat) Example 213 0.20 μm33.8 3.29 6.7 94% 6.80E−05 continuous film (flat) Example 214 0.20 μm35.0 3.68 6.4 94% 7.50E−05 continuous film (flat) Example 215 0.20 μm34.6 3.42 6.9 94% 4.89E−05 continuous film (flat) Example 216 0.20 μm34.8 3.58 6.5 95% 1.00E−04 continuous film (flat) Example 217 0.20 μm33.5 3.39 6.5 96% 4.90E−05 continuous film (flat) Example 218 0.20 μm33.3 3.64 6.5 95% 5.90E−05 continuous film (flat) Example 219 0.20 μm33.5 3.72 6.8 94% 6.30E−05 continuous film (flat) Example 220 0.20 μm34.2 3.19 6.9 96% 4.20E−05 continuous film (flat) Example 221 0.20 μm34.8 3.69 6.1 96% 6.90E−05 continuous film (flat) Example 222 0.20 μm34.0 3.00 6.6 96% 5.80E−05 continuous film (flat) Example 223 0.20 μm33.5 3.49 6.0 95% 3.60E−05 continuous film (flat) Example 224 0.20 μm33.5 3.44 6.3 97% 2.80E−05 continuous film (flat) Example 225 0.20 μm34.2 3.69 6.3 96% 4.90E−05 continuous film (flat) Example 226 0.20 μm34.5 4.19 6.4 95% 6.90E−05 continuous film (flat) Example 227 0.20 μm33.9 3:32 6.5 95% 3.60E−05 continuous film (flat) Example 228 0.20 μm33.5 3.29 6.6 96% 5.80E−05 continuous film (flat) Example 229 0.20 μm34.0 3.86 6.6 94% 7.90E−05 continuous film (flat) Example 230 0.20 μm34.5 3.23 6.3 95% 5.50E−05 continuous film (flat) Example 231 0.20 μm34.5 3.75 6.2 95% 6.90E−05 continuous film (flat) Example 232 0.20 μm35.8 3.69 6.2 96% 1.50E−04 continuous film (flat) Example 233 0.20 μm35.6 4.35 6.1 97% 6.90E−05 continuous film (flat) Example 234 0.20 μm34.2 3.47 6.2 96% 4.90E−05 continuous film (flat) Example 235 0.20 μm34.1 3.58 6.9 95% 6.30E−05 continuous film (flat) Example 236 0.20 μm34.0 3.19 6.8 95% 4.80E−05 continuous film (flat) Example 237 0.20 μm33.2 3.49 6.4 96% 3.90E−05 continuous film (flat) Example 238 0.20 μm33.5 3.69 6.8 94% 4.80E−05 continuous film (flat) Example 239 0.20 μm33.9 4.35 6.5 96% 8.70E−05 continuous film (flat) Example 240 0.20 μm34.5 3.21 6.1 96% 7.50E−05 continuous film (flat)

TABLE 1-9 Filter- ability (filter Trans- pore size Surface mittanceConduc- limit for tension Viscosity (FT = 200 nm, tivity passage) (mN/m)(mPa/S) PH λ = 550 nm) (S/cm) Spray-coated film state Comparative 0.45μm 60.0 3.55 2.1 93% 1.42E+00 droplet marks, Example 1 sea-islandstructure Comparative 0.45 μm 58.5 3.21 1.9 93% 2.56E+00 droplet marks,Example 2 sea-island structure Comparative 0.45 μm 57.7 3.63 2.0 94%1.89E+00 droplet marks, Example 3 sea-island structure Comparative 0.45μm 56.6 3.12 2.0 92% 2.00E+00 droplet marks, Example 4 sea-islandstructure Comparative 0.45 μm 56.2 3.46 1.8 97% 3.01E+00 droplet marks,Example 5 sea-island structure Comparative 0.45 μm 58.6 3.21 2.0 97%1.89E+00 droplet marks, Example 6 sea-island structure Comparative 0.45μm 57.7 3.83 1.8 95% 3.41E+00 droplet marks, Example 7 sea-islandstructure Comparative 0.45 μm 58.0 3.25 1.9 96% 3.25E+00 droplet marks,Example 8 sea-island structure Comparative 0.45 μm 57.7 3.40 1.9 94%9.53E-01 droplet marks, Example 9 sea-island structure Comparative 0.45μm 58.0 3.36 2.0 95% 5.36E+00 droplet marks, Example 10 sea-islandstructure Comparative 0.45 μm 51.0 4.74 7.0 93% 4.70E−05 partial film,spotted Example 11 Comparative 0.45 μm 51.2 5.00 6.4 95% 9.18E−05partial film, spotted Example 12 Comparative 0.45 μm 52.0 4.23 6.9 94%3.92E−05 partial film, spotted Example 13 Comparative 0.45 μm 53.2 4.016.8 95% 3.32E−05 partial film, spotted Example 14 Comparative 0.45 μm52.8 4.89 6.3 92% 1.11E−04 partial film, spotted Example 15 Comparative0.45 μm 53.5 4.56 6.9 92% 5.52E−05 partial film, spotted Example 16Comparative 0.45 μm 52.8 4.85 6.5 92% 1.12E−04 partial film, spottedExample 17 Comparative 0.45 μm 51.5 5.12 6.4 96% 8.87E−05 partial film,spotted Example 18 Comparative 0.45 μm 53.0 4.99 6.9 95% 6.75E−05partial film, spotted Example 19 Comparative 0.45 μm 52.1 4.88 6.9 93%1.07E−04 partial film, spotted Example 20

As shown in Tables 1-1 to 1-9, by the conductive compositions ofExamples 1 to 120, in each of which the water-soluble organic solvent(C) was added to the H₂O dispersion of the composite of the π-conjugatedpolymer (A) and the polymer (B) shown by the general formula (2)prepared by copolymerizing the polymerizable monomer shown by thegeneral formula (1) with the monomer having a fluorosulfonic acid, lowersurface tensions and viscosities were exhibited than those ofComparative Examples 1 to 10, and the filtration pore size limits wereas small as 0.20 μm. Moreover, regarding pH, transmittance, andconductivity, the performances were not degraded by adding thewater-soluble organic solvents (C). Meanwhile, in the coating test witha spray coater, continuous films (flat films) were formed on thesubstrates in Examples 1 to 120; in contrast, in Comparative Examples 1to 10, only sea-island structures attributable to the droplets andpartial films not completely covering the substrates were formed.

Similarly, in Examples 121 to 240, which are the compositions obtainedby adding the nonionic surfactant and the compound as the component (E)shown by the following general formula (3) to Examples 1 to 120, thesurface tensions and viscosities were lower than those of ComparativeExamples 11 to 20, and the filtration pore size limits were as small as0.20 μm. Further, adding the water-soluble organic solvents (C) did notresult in performance degradation of pH, transmittance, andconductivity. Furthermore, in the coating test with a spray coater,continuous films (flat films) were formed on the substrates in Examples121 to 240; in contrast, in Comparative Examples 11 to 20, only spottedand partial films not completely covering the substrates were formed.

The conductive compositions of Examples 1 to 240 and ComparativeExamples 1 to 20 were each mounted as a hole injection layer in anorganic EL device. The percentage of luminance decrease in each devicewas measured.

The conductive composition of Example 1 was applied to a washed glasssubstrate with ITO by spray coating to have a film thickness of 100 nm.α-NPD (diphenylnaphthyldiamine) was stacked thereon as a hole transportlayer by vapor deposition to have a film thickness of 80 nm. Then, as alight emitting layer, Alq₃ (tris(8-hydroxyquinoline)aluminum) complexwas vapor-deposited to have a film thickness of 35 nm, and 8-Liq(8-hydroxyquinolinolato-lithium) was vapor-deposited thereon to have afilm thickness of 30 nm. An electrode made of an alloy in whichmagnesium and silver had been mixed was formed thereon to have a filmthickness of 100 nm. Thus, an organic EL device was obtained. The devicewas caused to emit light in high load state with a fixed current densityof 20 mA/cm² to then measure the elapsed time until the luminance became70% of the initial luminance. Tables 2-1 to 2-9 show this result and theothers.

TABLE 2-1 Elapsed time (h) until 70% of initial luminance Example 1 3564Example 2 3258 Example 3 3599 Example 4 3843 Example 5 3699 Example 63211 Example 7 3002 Example 8 3485 Example 9 3658 Example 10 3755Example 11 3566 Example 12 3252 Example 13 3789 Example 14 3581 Example15 3936 Example 16 3867 Example 17 3800 Example 18 3772 Example 19 3962Example 20 3559 Example 21 3206 Example 22 3893 Example 23 3152 Example24 3356 Example 25 3077 Example 26 3552 Example 27 3789 Example 28 3581Example 29 3936 Example 30 3768

TABLE 2-2 Elapsed time (h) until 70% of initial luminance Example 313800 Example 32 3772 Example 33 3956 Example 34 3559 Example 35 3505Example 36 3896 Example 37 3152 Example 38 3569 Example 39 3077 Example40 3252 Example 41 3789 Example 42 3581 Example 43 3965 Example 44 3867Example 45 3800 Example 46 3772 Example 47 3961 Example 48 3559 Example49 3505 Example 50 3893 Example 51 3152 Example 52 3365 Example 53 3077Example 54 3252 Example 55 3556 Example 56 3581 Example 57 3936 Example58 3856 Example 59 3800 Example 60 3772

TABLE 2-3 Elapsed time (h) until 70% of initial luminance Example 613961 Example 62 3559 Example 63 3206 Example 64 3869 Example 65 3159Example 66 3362 Example 67 3088 Example 68 3856 Example 69 3695 Example70 3158 Example 71 3699 Example 72 3600 Example 73 3648 Example 74 3699Example 75 3559 Example 76 3258 Example 77 3695 Example 78 3458 Example79 3599 Example 80 3692 Example 81 3489 Example 82 3691 Example 83 3185Example 84 3956 Example 85 3644 Example 86 3005 Example 87 3963 Example88 3782 Example 89 3915 Example 90 3548

TABLE 2-4 Elapsed time (h) until 70% of initial luminance Example 913202 Example 92 3615 Example 93 3158 Example 94 3956 Example 95 3485Example 96 3694 Example 97 3158 Example 98 3698 Example 99 3648 Example100 3588 Example 101 3692 Example 102 3458 Example 103 3600 Example 1043158 Example 105 3598 Example 106 3699 Example 107 3158 Example 108 3754Example 109 3777 Example 110 3596 Example 111 3158 Example 112 3695Example 113 3655 Example 114 3158 Example 115 3964 Example 116 3485Example 117 2159 Example 118 3915 Example 119 3589 Example 120 3844

TABLE 2-5 Elapsed time (h) until 70% of initial luminance Example 1215596 Example 122 5648 Example 123 5961 Example 124 5358 Example 125 5555Example 126 5694 Example 127 5612 Example 128 6000 Example 129 5694Example 130 5998 Example 131 4961 Example 132 5559 Example 133 5206Example 134 5684 Example 135 5565 Example 136 5329 Example 137 5009Example 138 5252 Example 139 5486 Example 140 5788 Example 141 5956Example 142 5884 Example 143 5800 Example 144 5772 Example 145 5694Example 146 5102 Example 147 5206 Example 148 5893 Example 149 4999Example 150 5648

TABLE 2-6 Elapsed time (h) until 70% of initial luminance Example 1515666 Example 152 5361 Example 153 5489 Example 154 5984 Example 155 5936Example 156 5388 Example 157 5999 Example 158 5848 Example 159 5678Example 160 5754 Example 161 5632 Example 162 5777 Example 163 5121Example 164 5362 Example 165 5077 Example 166 5252 Example 167 5369Example 168 5488 Example 169 5699 Example 170 5325 Example 171 5777Example 172 5772 Example 173 4961 Example 174 5559 Example 175 5206Example 176 4893 Example 177 5648 Example 178 5869 Example 179 5963Example 180 5252

TABLE 2-7 Elapsed time (h) until 70% of initial luminance Example 1815477 Example 182 5989 Example 183 5488 Example 184 5399 Example 185 5777Example 186 5848 Example 187 5968 Example 188 5559 Example 189 5206Example 190 5798 Example 191 5456 Example 192 5318 Example 193 5077Example 194 5252 Example 195 5688 Example 196 5612 Example 197 5556Example 198 5468 Example 199 5328 Example 200 5969 Example 201 5486Example 202 5877 Example 203 5648 Example 204 5556 Example 205 5186Example 206 5318 Example 207 5789 Example 208 5999 Example 209 5485Example 210 5666

TABLE 2-8 Elapsed time (h) until 70% of initial luminance Example 2115484 Example 212 5286 Example 213 5800 Example 214 5772 Example 215 5444Example 216 5699 Example 217 5185 Example 218 5636 Example 219 5989Example 220 5462 Example 221 5596 Example 222 5699 Example 223 5483Example 224 5632 Example 225 5648 Example 226 5248 Example 227 5252Example 228 5648 Example 229 5255 Example 230 5559 Example 231 5666Example 232 5669 Example 233 5445 Example 234 5753 Example 235 5255Example 236 5635 Example 237 5485 Example 238 5956 Example 239 5358Example 240 5755

TABLE 2-9 Elapsed time (h) until 70% of initial luminance Comparativeunmeasurable (partial light emission, Example 1 non-uniform lightemission) Comparative unmeasurable (partial light emission, Example 2non-uniform light emission) Comparative unmeasurable (partial lightemission, Example 3 non-uniform light emission) Comparative unmeasurable(partial light emission, Example 4 non-uniform light emission)Comparative unmeasurable (partial light emission, Example 5 non-uniformlight emission) Comparative unmeasurable (partial light emission,Example 6 non-uniform light emission) Comparative unmeasurable (partiallight emission, Example 7 non-uniform light emission) Comparativeunmeasurable (partial light emission, Example 8 non-uniform lightemission) Comparative unmeasurable (partial light emission, Example 9non-uniform light emission) Comparative unmeasurable (partial lightemission, Example 10 non-uniform light emission) Comparativeunmeasurable (partial light emission, Example 11 non-uniform lightemission) Comparative unmeasurable (partial light emission, Example 12non-uniform light emission) Comparative unmeasurable (partial lightemission, Example 13 non-uniform light emission) Comparativeunmeasurable (partial light emission, Example 14 non-uniform lightemission) Comparative unmeasurable (partial light emission, Example 15non-uniform light emission) Comparative unmeasurable (partial lightemission, Example 16 non-uniform light emission) Comparativeunmeasurable (partial light emission, Example 17 non-uniform lightemission) Comparative unmeasurable (partial light emission, Example 18non-uniform light emission) Comparative unmeasurable (partial lightemission, Example 19 non-uniform light emission) Comparativeunmeasurable (partial light emission, Example 20 non-uniform lightemission)

As in the cases of the continuous films (flat films) formed on the glasssubstrates by using a spray coater shown in Tables 1-1 to 1-9,continuous films (flat) were formed on the glass substrates with ITO bythe conductive compositions of Examples 1 to 240, in each of which thewater-soluble organic solvent (C) was added to the H₂O dispersion of thecomposite of the n-conjugated polymer (A) and the polymer (B) shown bythe general formula (2) prepared by copolymerizing the polymerizablemonomer shown by the general formula (1) with the monomer having afluorosulfonic acid. Further, the organic EL devices in which thesefilms were mounted as the hole injection layers emitted uniform light,and the evaluation results of the percentage of luminance decrease(device lifetime) were obtained as shown in Tables 2-1 to 2-9. InExamples 1 to 120, since the compound (E) was not added, the H⁺diffusion from the films to adjacent layers was less suppressed, and thepercentages of luminance decrease (device lifetime) were less favorablethan Examples 120 to 240, but the organic EL devices emitted uniformlight. In contrast, in Comparative Examples 1 to 20, continuous films(flat) were not formed on the glass substrates with ITO, either, as inthe cases of the incomplete coating on the glass substrates by using aspray coater shown in Tables 1-1 to 1-9. The resulting organic ELdevices only exhibited partial light emission or non-uniform lightemission, and did not emit uniform light. Since uniform light was notemitted from the entire film surfaces, it was impossible to measure thepercentage of luminance decrease.

As described above, it was clarified that: the inventive conductivepolymer compositions have favorable filterability and highcontinuous-film formability on inorganic and organic substrates evenwhen a spray-type printer, such as a spray coater or inkjet, is used;the inventive conductive polymer compositions are capable of formingtransparent conductive films having favorable injection efficiency andappropriate conductivity as a hole injection layer. Moreover, in thecomponent (B), the repeating unit “b” containing a sulfo group iscopolymerized with the non-doping fluorinated unit “a” having nosulfonated terminal. The use of this polymer as a dopant to form acomposite with (A) improves the efficiency of eliminating residualmoisture in the formed film, and decreases extra non-doping sulfonatedterminals, consequently decreasing the H⁺ generation. When the inventiveconductive polymer compositions are employed as constituent films ofthin film-stacked devices, it is thus possible to suppress the influenceof H⁺ on other constituent layers. Further, adding the compound (E) canreduce the influence of H⁺ on other constituent layers. Such conductivepolymer compositions are revealed to have favorable affinity to highlyhydrophobic organic and inorganic substrates and have favorable filmformability on both types of the substrates with spray-type printers,such as a spray coater and inkjet.

Furthermore, the conductive films formed from such conductive polymercompositions are excellent in conductivity, hole injection efficiency,transparency, etc., and can reduce moisture volatilization from thefilms, aggregation, and so forth even when employed as constituent filmsof thin film-stacked devices. Thus, the conductive films are capable ofeffectively functioning as hole injection layers of the thinfilm-stacked devices.

It should be noted that the present invention is not limited to theabove-described embodiments. The embodiments are just examples, and anyembodiments that substantially have the same feature and demonstrate thesame functions and effects as those in the technical concept disclosedin claims of the present invention are included in the technical scopeof the present invention.

1-16. (canceled)
 17. A conductive polymer composition comprising: acomposite comprising a π-conjugated polymer (A), and a polymer (B) shownby the following general formula (2); H₂O (D) for dispersing thecomposite; and a water-soluble organic solvent (C),

wherein R¹ represents a hydrogen atom or a methyl group; Z representsany of a phenylene group, a naphthylene group, an ester group, an ethergroup, an amino group, and an amide group; when Z is a phenylene groupor a naphthylene group, R² represents any of a single bond and a linear,branched, or cyclic hydrocarbon group having 1 to 12 carbon atomsoptionally having one or both of an ester group and an ether group; whenZ is an ester group, an ether group, an amino group, or an amide group,R² represents any of a single bond and a linear, branched, or cyclichydrocarbon group having 1 to 14 carbon atoms optionally having an ethergroup; “m” represents any one of 1 to 3; R³, R⁵, and R⁷ eachindependently represent a hydrogen atom or a methyl group; R⁴ and R⁶each independently represent any of a single bond and a linear,branched, or cyclic hydrocarbon group having 1 to 12 carbon atomsoptionally having one or both of an ether group and an ester group; R⁸represents any of a single bond, a methylene group, an ethylidene group,an isopropylidene group, an ether group, an ester group, an amino group,an amide group, and a linear, branched, or cyclic hydrocarbon grouphaving 1 to 12 carbon atoms optionally containing an ether group, anester group, an amino group, an amide group, or a heteroatom, and theamino groups and the amide groups each optionally contain any of ahydrogen atom and a linear, branched, or cyclic hydrocarbon group having1 to 12 carbon atoms optionally containing a heteroatom; X₁ and X₂ eachindependently represent any of a single bond, a phenylene group, anaphthylene group, an ether group, an ester group, and an amide group;X₃ represents any of a single bond, an ether group, and an ester group;Rf₁ represents a fluorine atom or a trifluoromethyl group; “a”, b1, b2,and b3 satisfy 0<a<1.0, 0≤b1<1.0, 0≤b2<1.0, 0≤b3<1.0, and0<b1+b2+b3<1.0; and “n” represents an integer of 1 to
 4. 18. Theconductive polymer composition according to claim 17, wherein theconductive polymer composition has a surface tension in a range of 20 to50 mN/m.
 19. The conductive polymer composition according to claim 17,wherein the component (C) comprises an organic solvent (C1) having aboiling point of 120° C. or more and/or an organic solvent (C2) having aboiling point of less than 120° C. such that 1.0 wt %≤(C1)+(C2)≤50.0 wt% is satisfied relative to a total of the components (A), (B), and (D).20. The conductive polymer composition according to claim 18, whereinthe component (C) comprises an organic solvent (C1) having a boilingpoint of 120° C. or more and/or an organic solvent (C2) having a boilingpoint of less than 120° C. such that 1.0 wt %≤(C1)+(C2)≤50.0 wt % issatisfied relative to a total of the components (A), (B), and (D). 21.The conductive polymer composition according to claim 19, wherein thecomponents (C1) and (C2) are selected from alcohols, ethers, esters,ketones, and nitriles each of which has 1 to 7 carbon atoms.
 22. Theconductive polymer composition according to claim 20, wherein thecomponents (C1) and (C2) are selected from alcohols, ethers, esters,ketones, and nitriles each of which has 1 to 7 carbon atoms.
 23. Theconductive polymer composition according to claim 17, wherein therepeating unit “a” in the component (B) comprises one or more selectedfrom repeating units a1 to a4 shown by the following general formulae(4-1) to (4-4),

wherein R¹⁶, R¹⁷, R¹⁸, and R¹⁹ each independently represent a hydrogenatom or a methyl group; R²⁰ represents any of a single bond and alinear, branched, or cyclic hydrocarbon group having 1 to 14 carbonatoms optionally having an ether group; R¹⁵ represents any of a singlebond, a methylene group, an ethylidene group, an isopropylidene group,an ether group, an ester group, an amino group, an amide group, and alinear, branched, or cyclic hydrocarbon group having 1 to 12 carbonatoms optionally containing an ether group, an ester group, an aminogroup, an amide group, or a heteroatom, and the amino groups and theamide groups each optionally contain any of a hydrogen atom and alinear, branched, or cyclic hydrocarbon group having 1 to 12 carbonatoms optionally containing a heteroatom; Y represents any of an ethergroup, an ester group, an amino group, and an amide group, and the aminogroup and the amide group each optionally contain any of a hydrogen atomand a linear, branched, or cyclic hydrocarbon group having 1 to 12carbon atoms optionally containing a heteroatom; “m” represents any oneof 1 to 3; and a1, a2, a3, and a4 satisfy 0≤a1<1.0, 0≤a2<1.0, 0≤a3<1.0,0≤a4<1.0, and 0<a1+a2+a3+a4<1.0.
 24. The conductive polymer compositionaccording to claim 18, wherein the repeating unit “a” in the component(B) comprises one or more selected from repeating units a1 to a4 shownby the following general formulae (4-1) to (4-4),

wherein R¹⁶, R¹⁷, R¹⁸, and R¹⁹ each independently represent a hydrogenatom or a methyl group; R²⁰ represents any of a single bond and alinear, branched, or cyclic hydrocarbon group having 1 to 14 carbonatoms optionally having an ether group; R¹⁵ represents any of a singlebond, a methylene group, an ethylidene group, an isopropylidene group,an ether group, an ester group, an amino group, an amide group, and alinear, branched, or cyclic hydrocarbon group having 1 to 12 carbonatoms optionally containing an ether group, an ester group, an aminogroup, an amide group, or a heteroatom, and the amino groups and theamide groups each optionally contain any of a hydrogen atom and alinear, branched, or cyclic hydrocarbon group having 1 to 12 carbonatoms optionally containing a heteroatom; Y represents any of an ethergroup, an ester group, an amino group, and an amide group, and the aminogroup and the amide group each optionally contain any of a hydrogen atomand a linear, branched, or cyclic hydrocarbon group having 1 to 12carbon atoms optionally containing a heteroatom; “m” represents any oneof 1 to 3; and a1, a2, a3, and a4 satisfy 0≤a1<1.0, 0≤a2<1.0, 0≤a3<1.0,0≤a4<1.0, and 0<a1+a2+a3+a4<1.0.
 25. The conductive polymer compositionaccording to claim 17, wherein the repeating unit b1 in the component(B) comprises one or more selected from repeating units b′1 to b′4 shownby the following general formulae (5-1) to (5-4),

wherein R²¹, R²², R²³, and R²⁴ each independently represent a hydrogenatom or a methyl group; and b′ 1, b′2, b′3, and b′4 satisfy 0≤b′1<1.0,0≤b′2<1.0, 0≤b′3<1.0, 0≤b′4<1.0, and 0<b′1+b′2+b′3+b′4<1.0.
 26. Theconductive polymer composition according to claim 18, wherein therepeating unit b1 in the component (B) comprises one or more selectedfrom repeating units b′ 1 to b′4 shown by the following general formulae(5-1) to (5-4),

wherein R²¹, R²², R²³, and R²⁴ each independently represent a hydrogenatom or a methyl group; and b′ 1, b′2, b′3, and b′4 satisfy 0≤b′1<1.0,0≤b′2<1.0, 0≤b′3<1.0, 0≤b′4<1.0, and 0<b′1+b′2+b′3+b′4<1.0.
 27. Theconductive polymer composition according to claim 17, wherein thecomponent (B) further comprises a repeating unit “c” shown by thefollowing general formula (6),

wherein “c” satisfies 0<c<1.0.
 28. The conductive polymer compositionaccording to claim 17, wherein the component (B) has a weight-averagemolecular weight in a range of 1,000 to 500,000.
 29. The conductivepolymer composition according to claim 17, wherein the component (A) isa material in which at least one precursor monomer selected from thegroup consisting of pyrrole, thiophene, selenophene, tellurophene,aniline, polycyclic aromatic compounds, and derivatives thereof ispolymerized.
 30. The conductive polymer composition according to claim17, comprising a compound (E) shown by the following general formula(3),

wherein R²⁰¹ and R²⁰² each independently represent any of a hydrogenatom, a heteroatom, and a linear, branched, or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms optionally having aheteroatom; R²⁰³ and R²⁰⁴ each independently represent any of a hydrogenatom and a linear, branched, or cyclic monovalent hydrocarbon grouphaving 1 to 20 carbon atoms optionally having a heteroatom; R²⁰¹ andR²⁰³, or R²⁰¹ and R²⁰⁴, are optionally bonded to each other to form aring; L represents a linear, branched, or cyclic tetravalent organicgroup having 1 to 20 carbon atoms optionally having a heteroatom; andwhen L has a heteroatom, the heteroatom is optionally an ion.
 31. Theconductive polymer composition according to claim 30, wherein thecomponent (E) is contained in an amount of 1 part by mass to 50 parts bymass based on 100 parts by mass of the composite of the component (A)with the component (B).
 32. The conductive polymer composition accordingto claim 17, further comprising a nonionic surfactant.
 33. Theconductive polymer composition according to claim 32, wherein thenonionic surfactant is contained in an amount of 1 part by mass to 15parts by mass based on 100 parts by mass of the composite of thecomponent (A) with the component (B).
 34. The conductive polymercomposition according to claim 17, wherein the conductive polymercomposition is used to form a hole injection layer of an organic ELdevice.
 35. A substrate comprising an organic EL device, wherein theorganic EL device comprises a hole injection layer formed from theconductive polymer composition according to claim
 17. 36. A method forproducing the substrate according to claim 35, comprising a step ofapplying the conductive polymer composition by employing a spray coateror inkjet printing.